U.S. patent number 9,746,771 [Application Number 15/048,187] was granted by the patent office on 2017-08-29 for laminate body.
This patent grant is currently assigned to FUJIFILM Corporation. The grantee listed for this patent is FUJIFILM CORPORATION. Invention is credited to Yu Iwai, Yoshitaka Kamochi, Ichiro Koyama, Atsushi Nakamura.
United States Patent |
9,746,771 |
Kamochi , et al. |
August 29, 2017 |
Laminate body
Abstract
There is provided a laminate body which is capable of forming an
excellent pattern on an organic semiconductor. A laminate body
includes at least a water-soluble resin film and a resist film
formed of a chemically amplified photosensitive resin composition
on a surface of an organic semiconductor film in this order, in
which the chemically amplified photosensitive resin composition
contains a photoacid generator which is decomposed in an amount of
80% by mole or greater when exposed to light under the condition of
100 mJ/cm.sup.2 or greater at a wavelength of 365 nm, a mask
pattern is formed by an exposed portion being hardly soluble in a
developer containing an organic solvent, and the formed mask
pattern is used as an etching mask.
Inventors: |
Kamochi; Yoshitaka
(Haibara-gun, JP), Koyama; Ichiro (Haibara-gun,
JP), Iwai; Yu (Haibara-gun, JP), Nakamura;
Atsushi (Haibara-gun, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM CORPORATION |
Tokyo |
N/A |
JP |
|
|
Assignee: |
FUJIFILM Corporation (Tokyo,
JP)
|
Family
ID: |
52483720 |
Appl.
No.: |
15/048,187 |
Filed: |
February 19, 2016 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20160170303 A1 |
Jun 16, 2016 |
|
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
PCT/JP2014/071977 |
Aug 22, 2014 |
|
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Aug 23, 2013 [JP] |
|
|
2013-173374 |
Mar 28, 2014 [JP] |
|
|
2014-068595 |
Aug 21, 2014 [JP] |
|
|
2014-168415 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G03F
7/0397 (20130101); G03F 7/0046 (20130101); G03F
7/325 (20130101); G03F 7/0392 (20130101); G03F
7/11 (20130101); G03F 7/0382 (20130101); G03F
7/0045 (20130101) |
Current International
Class: |
G03F
7/11 (20060101); G03F 7/038 (20060101); G03F
7/32 (20060101); G03F 7/004 (20060101); G03F
7/039 (20060101) |
Field of
Search: |
;430/270.1,271.1,273.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
2004-266197 |
|
Sep 2004 |
|
JP |
|
2006-041317 |
|
Feb 2006 |
|
JP |
|
2006-058497 |
|
Mar 2006 |
|
JP |
|
2014-098889 |
|
May 2014 |
|
JP |
|
WO 2015064603 |
|
May 2015 |
|
JP |
|
10-2012-0123224 |
|
Nov 2012 |
|
KR |
|
Other References
Machine translation of WO 2015/064603 (no date). cited by examiner
.
International Preliminary Report on Patentability dated Mar. 3,
2016 from the International Bureau in counterpart International
Application No. PCT/JP2014/071977. cited by applicant .
International Search Report of PCT/JP2014/071977, dated Nov. 11,
2014. [PCT/ISA/210]. cited by applicant .
Written Opinion of PCT/JP2014/071977, dated Nov. 11, 2014.
[PCT/ISA/237]. cited by applicant .
Extended European Search Report dated Sep. 6, 2016 from the
European Patent Office in counterpart European Application No.
14838350.8. cited by applicant .
Office Action dated Jun. 1, 2017 from the Korean Intellectual
Property Office in counterpart Korean Application No.
10-2016-7004417. cited by applicant.
|
Primary Examiner: Walke; Amanda C
Attorney, Agent or Firm: Sughrue Mion, PLLC
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Continuation of PCT International Application
No. PCT/JP2014/071977 filed on Aug. 22, 2014, which claims priority
under 35 U.S.C .sctn.119(a) to Japanese Patent Application No.
2013-173374 filed on Aug. 23, 2013, Japanese Patent Application No.
2014-068595 filed on Mar. 28, 2014 and Japanese Patent Application
No. 2014-168415 filed on Aug. 21, 2014. Each of the above
application(s) is hereby expressly incorporated by reference, in
its entirety, into the present application.
Claims
What is claimed is:
1. A laminate body which includes, in order, a substrate, an
organic semiconductor film, a water-soluble resin film and a resist
film formed of a chemically amplified photosensitive resin
composition, wherein the chemically amplified photosensitive resin
composition contains a photoacid generator which decomposes in an
amount of 80% by mole or greater when exposed to light under the
condition of 100 mJ/cm.sup.2 at a wavelength of 365 nm, such that
the resin composition is capable of forming a mask pattern for an
etching mask as a result of exposed portions being hardly soluble
in a developer containing an organic solvent.
2. The laminate body according to claim 1, wherein the sp value of
a water-soluble resin of the water-soluble resin film is equal to
or greater than 18 (MPa).sup.1/2 and less than 29
(MPa).sub.1/2.
3. The laminate body according to claim 1, wherein the sp value of
a water-soluble resin of the water-soluble resin film is in a range
of 20 (MPa).sup.1/2 to 26 (MPa).sup.1/2.
4. The laminate body according to claim 1, wherein the
water-soluble resin of the water-soluble resin film is polyvinyl
alcohol, polyvinylpyrrolidone, or a mixture of polyvinyl alcohol
and polyvinylpyrrolidone.
5. The laminate body according to claim 1, wherein the chemically
amplified photosensitive resin composition is a resin composition
whose polarity changes and which becomes hardly soluble in an
organic solvent having an sp value of less than 18 (MPa).sup.1/2
when it is exposed to light under the condition of 100 mJ/cm.sup.2
or greater at a wavelength of 365 nm.
6. The laminate body according to claim 1, wherein the chemically
amplified photosensitive resin composition includes a resin having
a cyclic ether ester structure.
7. The laminate body according to claim 1, wherein the chemically
amplified photosensitive resin composition includes a resin having
a repeating unit that contains a group represented by the following
Formula (11); ##STR00098## wherein in Formula (11), R.sup.1
represents a hydrogen atom or an alkyl group, L.sup.1 represents a
carbonyl group or a phenylene group, and R.sup.21 to R.sup.27 each
independently represents a hydrogen atom or an alkyl group.
8. The laminate body according to claim 1, wherein the chemically
amplified photosensitive resin composition includes a resin having
a repeating unit represented by the following Formula (B.sup.1-1);
##STR00099## wherein in Formula (B.sup.1-1), R.sup.1 represents a
hydrogen atom, an alkyl group, a cyano group, or a halogen atom;
R.sup.2 to R.sup.4 each independently represents an alkyl group;
and two of R.sup.2 to R.sup.4 may be bonded to each other to form a
cyclic alkyl group.
9. The laminate body according to claim 1, wherein the chemically
amplified photosensitive resin composition includes a resin having
a repeating unit represented by the following Formula (B.sup.1-2);
##STR00100## wherein in Formula (B.sup.1-2), R.sup.1 represents a
hydrogen atom, an alkyl group, a cyano group, or a halogen atom;
R.sup.2 to R.sup.4 each independently represents an alkyl group;
two of R.sup.2 to R.sup.4 may be bonded to each other to form a
cyclic alkyl group; and R.sup.5 represents a divalent chain-like
hydrocarbon group.
10. The laminate body according to claim 1, wherein the photoacid
generator is a non-ionic photoacid generator which generates acids
having a pKa of -6 or less using irradiation with active rays or
radiation and whose molar absorption coefficient at a wavelength of
365 nm is 4000 L/(molcm) or greater.
11. The laminate body according to claim 10, wherein the non-ionic
photoacid generator is a compound which includes a fluoroalkyl
group having 2 or 3 carbon atoms and is a compound which generates
a sulfonic acid including a fluoroalkyl group having 2 or 3 carbon
atoms using irradiation with active rays and/or radiation.
12. The laminate body according to claim 10, wherein the non-ionic
photoacid generator is a compound represented by the following
Formula (3); ##STR00101## wherein in Formula (3), R.sup.6
represents a fluoroalkyl group having 2 or 3 carbon atoms; and
R.sup.7 represents an alkylene group, an alkenylene group, or an
arylene group.
13. The laminate body according to claim 10, wherein the non-ionic
photoacid generator is a compound which includes a 5-membered ring
imide sulfonate group.
14. The laminate body according to claim 10, wherein the non-ionic
photoacid generator is a compound represented by the following
Formula (4); ##STR00102## wherein in Formula (4), R.sup.8
represents a fluoroalkyl group having 2 or 3 carbon atoms; R.sup.9
represents an alkyl group having 1 to 8 carbon atoms or a
fluoroalkyl group; and R.sup.10 represents an aromatic hydrocarbon
group or an aromatic heterocyclic group.
15. The laminate body according to claim 1, wherein the photoacid
generator is a compound which includes an oxime sulfonate
group.
16. The laminate body according to claim 1, wherein the chemically
amplified photosensitive resin composition further includes a basic
compound.
17. The laminate body according to claim 16, wherein the basic
compound is a primary amine compound.
18. The laminate body according to claim 1, wherein the chemically
amplified photosensitive resin composition further includes a resin
including a repeating unit represented by the following Formula
(B.sup.1-1) and/or a repeating unit represented by the following
Formula (B.sup.1-2), and a basic compound, and the photoacid
generator is a non-ionic photoacid generator which generates acids
having a pKa of -6 or less using irradiation with active rays or
radiation and whose molar absorption coefficient at a wavelength of
365 nm is 4000 L/(molcm) or greater; ##STR00103## wherein in
Formula (B.sup.1-1), R.sup.1 represents a hydrogen atom, an alkyl
group, a cyano group, or a halogen atom; R.sup.2 to R.sup.4 each
independently represent an alkyl group; and two of R.sup.2 to
R.sup.4 may be bonded to each other to form a cyclic alkyl group,
##STR00104## wherein in Formula (B.sup.1-2), R.sup.1 represents a
hydrogen atom, an alkyl group, a cyano group, or a halogen atom;
R.sup.2 to R.sup.4 each independently represents an alkyl group;
two of R.sup.2 to R.sup.4 may be bonded to each other to form a
cyclic alkyl group; and R.sup.5 represents a divalent chain-like
hydrocarbon group.
19. The laminate body according to claim 1, wherein the chemically
amplified photosensitive resin composition is a negative type
composition.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a laminate body and particularly
relates to a laminate body of a resist composition.
2. Description of the Related Art
In recent years, electronic devices using an organic semiconductor
have been widely used. An organic semiconductor has an advantage
that it can be manufactured by a simpler process than that of a
device using an inorganic semiconductor such as silicon of the
related art. In addition, it is considered that material
characteristics can be easily changed by changing the molecular
structure, the variations of materials are abundant, and functions
or elements which have not been obtained by an inorganic
semiconductor can be realized. For example, an organic
semiconductor can be applied to electronic devices such as an
organic solar cell, an organic electroluminescence device, an
organic light detector, an organic field effect transistor, an
organic electroluminescence light emitting device, a gas sensor, an
organic rectifier device, an organic inverter, and an information
recording device.
Patterning of an organic semiconductor has been performed using
printing technology, but there is a limit to fine processing when
the patterning is performed using printing technology. Further, the
organic semiconductor tends to be easily damaged.
JP2006-41317A discloses a method of patterning an organic
semiconductor layer including: a process of forming an organic
semiconductor layer; a process of laminating and forming a
protective layer that protects the organic semiconductor layer from
a mask layer on the organic semiconductor layer; a process of
laminating and forming a mask layer having a predetermined pattern
on the protective layer; and a process of patterning the protective
layer and the organic semiconductor layer to have the same shape by
performing etching that makes the mask layer into a mask, in which
the protective layer is formed by an organic polymer compound or an
insulating inorganic compound which is a material different from
that of the mask layer and has hydrophilicity.
JP2004-266197A discloses that a photosensitive composition such as
a photosensitive resin layer is formed on an organic semiconductor
protective layer using a material which does not affect an organic
semiconductor layer.
A method of the related art has a problem in that a mask layer
remains as a protective layer after patterning is finished.
The present invention has been made to solve the above-described
problem and an object thereof is to provide a laminate body which
is capable of forming an excellent pattern.
SUMMARY OF THE INVENTION
As a result of intensive research, the present inventors found that
patterning can be performed without damaging an organic
semiconductor by forming a water-soluble resin film and a resist
film formed of a chemically amplified photosensitive resin
composition on one surface of an organic semiconductor in this
order and performing etching after the resist film is patterned,
thereby completing the present invention.
Specifically, the above-described problem has been solved by the
following means <1> or preferably by <2> to
<23>.
<1> A laminate body which includes at least a water-soluble
resin film and a resist film formed of a chemically amplified
photosensitive resin composition on a surface of an organic
semiconductor film in this order, in which the chemically amplified
photosensitive resin composition contains a photoacid generator
which is decomposed in an amount of 80% by mole or greater when
exposed to light under the condition of 100 mJ/cm.sup.2 or greater
at a wavelength of 365 nm, a mask pattern is formed by an exposed
portion being hardly soluble in a developer containing an organic
solvent, and the formed mask pattern is used as an etching
mask.
<2> The laminate body according to <1>, in which the
etching is dry etching.
<3> The laminate body according to <1>, in which the
etching is wet etching.
<4> The laminate body according to any one of <1> to
<3>, in which the sp value of a water-soluble resin of the
water-soluble resin film is equal to or greater than 18
(MPa).sup.1/2 and less than 29 (MPa).sup.1/2.
<5> The laminate body according to any one of <1> to
<3>, in which the sp value of a water-soluble resin of the
water-soluble resin film is in a range of 20 (MPa).sup.1/2 to 26
(MPa).sup.1/2.
<6> The laminate body according to any one of <1> to
<5>, in which the water-soluble resin of the water-soluble
resin film is polyvinyl alcohol, polyvinylpyrrolidone, or a mixture
of polyvinyl alcohol and polyvinylpyrrolidone.
<7> The laminate body according to any one of <1> to
<5>, in which the water-soluble resin of the water-soluble
resin film is polyvinylpyrrolidone.
<8> The laminate body according to any one of <1> to
<7>, in which when the chemically amplified photosensitive
resin composition is exposed to light under the condition of 100
mJ/cm.sup.2 or greater at a wavelength of 365 nm, the polarity
thereof is changed, and the chemically amplified photosensitive
resin composition becomes hardly soluble in an organic solvent
having an sp value of less than 18 (MPa).sup.1/2.
<9> The laminate body according to any one of <1> to
<8>, in which the chemically amplified photosensitive resin
composition includes a resin having a cyclic ether ester
structure.
<10> The laminate body according to any one of <1> to
<8>, in which the chemically amplified photosensitive resin
composition includes a resin having a repeating unit that contains
a group represented by the following Formula (11);
##STR00001##
in Formula (11), R.sup.1 represents a hydrogen atom or an alkyl
group, L.sup.1 represents a carbonyl group or a phenylene group,
and R.sup.21 to R.sup.27 each independently represent a hydrogen
atom or an alkyl group.
<11> The laminate body according to any one of <1> to
<10>, in which the chemically amplified photosensitive resin
composition includes a resin having a repeating unit represented by
the following Formula (B.sup.1-1);
##STR00002##
in Formula (B.sup.1-1), R.sup.1 represents a hydrogen atom, an
alkyl group, a cyano group, or a halogen atom; R.sup.2 to R.sup.4
each independently represent an alkyl group; and two of R.sup.2 to
R.sup.4 may be bonded to each other to form a cyclic alkyl
group.
<12> The laminate body according to any one of <1> to
<11>, in which the chemically amplified photosensitive resin
composition includes a resin having a repeating unit represented by
the following Formula (B.sup.1-2);
##STR00003##
in Formula (B.sup.1-2), R.sup.1 represents a hydrogen atom, an
alkyl group, a cyano group, or a halogen atom; R.sup.2 to R.sup.4
each independently represent an alkyl group; two of R.sup.2 to
R.sup.4 may be bonded to each other to form a cyclic alkyl group;
and R.sup.5 represents a divalent chain-like hydrocarbon group.
<13> The laminate body according to any one of <1> to
<12>, in which the photoacid generator is a non-ionic
photoacid generator which generates an acid having a pKa of -6 or
less using irradiation with active rays or radiation and whose
molar absorption coefficient at a wavelength of 365 nm is 4000
L/(molcm) or greater.
<14> The laminate body according to <13>, in which the
non-ionic photoacid generator is a compound which includes a
fluoroalkyl group having 2 or 3 carbon atoms and is a compound
which generates a sulfonic acid including a fluoroalkyl group
having 2 or 3 carbon atoms using irradiation with active rays
and/or radiation.
<15> The laminate body according to <13> or <14>,
in which the non-ionic photoacid generator is a compound
represented by the following Formula (3);
##STR00004##
in Formula (3), R.sup.6 represents a fluoroalkyl group having 2 or
3 carbon atoms; and R.sup.7 represents an alkylene group, an
alkenylene group, or an arylene group.
<16> The laminate body according to any one of <13> to
<15>, in which the non-ionic photoacid generator is a
compound which includes a 5-membered ring imide sulfonate
group.
<17> The laminate body according to <13> or <14>,
in which the non-ionic photoacid generator is a compound
represented by the following Formula (4);
##STR00005##
in Formula (4), R.sup.8 represents a fluoroalkyl group having 2 or
3 carbon atoms; R.sup.9 represents an alkyl group having 1 to 8
carbon atoms or a fluoroalkyl group; and R.sup.11 represents an
aromatic hydrocarbon group or an aromatic heterocyclic group.
<18> The laminate body according to any one of <1> to
<14>, in which the photoacid generator is a compound which
includes an oxime sulfonate group.
<19> The laminate body according to any one of <1> to
<18>, in which the chemically amplified photosensitive resin
composition further includes a basic compound.
<20> The laminate body according to <19>, in which the
basic compound is a primary amine compound.
<21> The laminate body according to any one of <1> to
<8>, in which the chemically amplified photosensitive resin
composition further includes a resin including a repeating unit
represented by the following Formula (B.sup.1-1) and/or a repeating
unit represented by the following Formula (B.sup.1-2), and a basic
compound, and the photoacid generator is a non-ionic photoacid
generator which generates an acid having a pKa of -6 or less using
irradiation with active rays or radiation and whose molar
absorption coefficient at a wavelength of 365 nm is 4000 L/(molcm)
or greater;
##STR00006##
in Formula (B.sup.1-1), R.sup.1 represents a hydrogen atom, an
alkyl group, a cyano group, or a halogen atom; R.sup.2 to R.sup.4
each independently represent an alkyl group; and two of R.sup.2 to
R.sup.4 may be bonded to each other to form a cyclic alkyl
group;
##STR00007##
in Formula (B.sup.1-2), R.sup.1 represents a hydrogen atom, an
alkyl group, a cyano group, or a halogen atom; R.sup.2 to R.sup.4
each independently represent an alkyl group; two of R.sup.2 to
R.sup.4 may be bonded to each other to form a cyclic alkyl group;
and R.sup.5 represents a divalent chain-like hydrocarbon group.
<22> The laminate body according to any one of <1> to
<21>, in which the chemically amplified photosensitive resin
composition is a negative type composition.
<23> The laminate body according to any one of <1> to
<22>, further including a substrate on the opposite side of
the organic semiconductor film to the side on which the
water-soluble resin film is laminated.
According to the present invention, it is possible to provide a
laminate body which is capable of forming an excellent pattern.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a process view illustrating an example of a method of
obtaining a substrate in which an organic semiconductor film is
patterned.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The constituent elements in the present invention described below
will be described based on representative embodiments of the
present invention, but the present invention is not limited to such
embodiments.
In regard to notation of a group (atomic group) in the present
specification, in a case where it is not noted whether a group
includes a substituent or not, it means that a group with a
substituent and a group without a substituent are both included.
For example, when an "alkyl group" is noted, an alkyl group without
a substituent (unsubstituted alkyl group) as well as an alkyl group
with a substituent (substituted alkyl group) are included.
In addition, "active rays" in the present specification mean, for
example, a line spectrum of a mercury lamp, far-ultraviolet rays
represented by an excimer laser, extreme ultraviolet rays (EUV
light), X-rays, and electron beams. In addition, the light in the
present invention indicates active rays or radiation. Further,
"exposure to light" in the present specification, unless otherwise
specified, includes not only exposure to a mercury lamp,
far-ultraviolet rays represented by excimer light, X-rays, or EUV
light but also drawings using particle beams such as electron beams
or ion beams.
The numerical ranges expressed using "to" in the present
specification indicate the ranges including the numerical values
described before and after "to" as the lower limits and the upper
limits.
Moreover, in the present specification, "(meth)acrylate" indicates
both or one of acrylate and methacrylate, "(meth)acryl" indicates
both or one of acryl and methacryl, and "(meth)acryloyl indicates
both or one of acryloyl and methacryloyl.
"Processes" in the present specification include not only
independent processes but also processes whose intended actions are
achieved even in a case where the processes cannot be precisely
distinguished from other processes.
The solid content concentration in the present specification
indicates a weight percentage of a weight of other components from
which a solvent is removed to the total weight of a composition.
The solid content indicates a solid content at 25.degree. C.
In the present specification, the weight average molecular weight
is defined as a value obtained by GPC measurement in terms of
polystyrene. In the present specification, a weight average
molecular weight (Mw) and a number average molecular weight (Mn)
can be acquired, for example, using an HLC-8220 (manufactured by
TOSOH CORPORATION), and a TSKgel Super AWM-H (6.0 mm ID.times.15.0
cm manufactured by TOSOH CORPORATION) as a column. The measurement
is carried out using 10 mmol/L lithium bromide NMP
(N-methylpyrrolidinone) solution as an eluent unless otherwise
noted.
<Laminate Body>
A laminate body of the present invention includes at least a
water-soluble resin film (1) and a resist film formed of a
chemically amplified photosensitive resin composition (2) on a
surface of an organic semiconductor film in this order, in which
the chemically amplified photosensitive resin composition (2)
contains a photoacid generator which is decomposed in an amount of
80% by mole or greater when exposed to light under the condition of
100 mJ/cm.sup.2 or greater at a wavelength of 365 nm, a mask
pattern is formed by an exposed portion of the chemically amplified
photosensitive resin composition being hardly soluble in a
developer containing an organic solvent, and the formed mask
pattern is used as an etching mask. Here, for example, etching may
be dry etching or wet etching as described below.
When a normal resist film is formed on an organic semiconductor
formed on a substrate and patterning is performed, the organic
semiconductor is easily dissolved in an organic solvent contained
in a resist and the organic semiconductor film is damaged.
On the contrary, in the present invention, a water-soluble resin
film is formed on an organic semiconductor as a protective film and
then a resist film is formed thereon. In this case, since the
resist and the organic semiconductor are not in direct contact, it
is possible to prevent the organic semiconductor from being
damaged. In addition, since the resist film uses a chemically
amplified photosensitive resin composition, long storage stability
and fine pattern formability can be achieved.
Hereinafter, the present invention will be described in detail.
<<Organic Semiconductor Film>>
The organic semiconductor film used in the present invention
indicates a film containing an organic material showing
characteristics of a semiconductor. Similar to a case of a
semiconductor formed of an inorganic material, there is a p-type
organic semiconductor that conducts positive holes as a carrier and
an n-type organic semiconductor that conducts electrons as a
carrier. The flowability of a carrier in the organic semiconductor
is expressed as a carrier mobility .mu.. Depending on the
applications, the mobility is normally high, preferably 10.sup.-7
cm.sup.2/Vs or greater, more preferably 10.sup.-6 cm.sup.2/Vs or
greater, and still more preferably 10.sup.-5 cm.sup.2/Vs or
greater. The mobility can be acquired by characteristics or a
time-of-flight measurement (TOF) at the time of preparation of a
field effect transistor (FET) element.
Typically, it is preferable that the organic semiconductor film is
used by being formed on a substrate. That is, it is preferable that
the substrate is formed on a surface which is the opposite side to
a side on which the water-soluble resin film of the organic
semiconductor film is laminated. As the substrate which can be used
in the present invention, various materials, for example, silicon,
quartz, ceramic, glass, a polyester film such as polyethylene
naphthalene (PEN) or polyethylene terephthalate (PET), and a
polyimide film can be used and any substrate may be selected
according to the application thereof. For example, in a case where
a flexible element is required, a flexible substrate can be used.
Moreover, the thickness of the substrate is not particularly
limited.
Any of an organic semiconductor material and an inorganic
semiconductor material may be used as the p-type semiconductor
material which can be used as long as the material shows hole
transporting properties, preferred examples thereof include a
p-type ic conjugated polymer (for example, substituted or
unsubstituted polythiophene (for example, poly(3-hexylthiophene)
(P3HT)), polyselenophene, polypyrrole, polyparaphenylene,
polyparaphenylene vinylene, polythiophene vinylene, or
polyaniline), a condensed polycyclic compound (for example,
substituted or unsubstituted anthracene, tetracene, pentacene,
anthrathiophene, or hexabenzocoronene), a triarylamine compound
(for example, m-MTDATA, 2-TNATA, NPD, TPD, mCP, or CBP), a
5-membered heterocyclic compound (for example, a substituted or
unsubstituted oligothiophene or TTF), a phthalocyanine compound
(various substituted or unsubstituted central metals such as
phthalocyanine, naphthalocyanine, anthracyanine, or
tetrapyrazinoporphyrazine), a porphyrin compound (various
substituted or unsubstituted central metals such as porphyrin),
carbon nanotubes, a semiconductor polymer modified with carbon
nanotubes, and graphene; more preferred examples thereof include a
p-type .pi. conjugated polymer, a condensed polycyclic compound, a
triarylamine compound, a 5-membered heterocyclic compound, a
phthalocyanine compound, and a porphyrin compound; and still more
preferred examples thereof include a p-type .pi. conjugated
polymer.
Any of an organic semiconductor material and an inorganic
semiconductor material may be used as the n-type semiconductor
material which can be used as a semiconductor material as long as
the material shows hole transporting properties, preferred examples
thereof including a fullerene compound, an electron deficient
phthalocyanine compound, a naphthalene tetracarbonyl compound, a
perylene tetracarbonyl compound, a TCNQ compound, an n-type .pi.
conjugated polymer, and an n-type inorganic semiconductor; more
preferred examples thereof including a fullerene compound, an
electron deficient phthalocyanine compound, a naphthalene
tetracarbonyl compound, a perylene tetracarbonyl compound, and a
.pi. conjugated polymer; and particularly preferred examples
including a fullerene compound and a .pi. conjugated polymer. In
the present invention, a fullerene compound indicates a substituted
or unsubstituted fullerene compound and any of C.sub.60, C.sub.70,
C.sub.76, C.sub.78, C.sub.80, C.sub.82, C.sub.84, C.sub.86,
C.sub.88, C.sub.90, C.sub.96, C.sub.116, C.sub.180, C.sub.240, and
C.sub.540 may be used as a fullerene. As the fullerene compound,
substituted or unsubstituted C.sub.60, C.sub.70, or C.sub.86 is
preferable and PCBM ([6,6]-phenyl-C.sub.61-butyric acid methyl
ester) or an analog thereof (a compound obtained by substituting
the C.sub.60 portion with C.sub.70 or C.sub.86; a compound obtained
by substituting the benzene ring substituent with another aromatic
ring or a hetero ring; or a compound obtained by substituting
methyl ester with n-butyl ester or i-butyl ester) is particularly
preferable. Examples of electron deficient phthalocyanines include
those formed by four or more electron withdrawing groups being
bonded to various central metal atoms such as phthalocyanine
(F.sub.16MPc, FPc-S8, or the like), naphthalocyanine,
anthracyanine, and substituted or unsubstituted
tetrapyrazinoporphyrazine. The naphthalene tetracarbonyl compound
is not particularly limited, and a naphthalene tetracarboxylic
anhydride (NTCDA), a naphthalene bisimide compound (NTCDI), or a
perinone pigment (Pigment Orange 43, Pigment Red 194, or the like)
is preferable. The perylene tetracarbonyl compound is not
particularly limited, and a perylene tetracarboxylic anhydride
(PTCDA), a perylene bisimide compound (PTCDI), or a benzimidazole
condensed ring (PV) is preferable. The TCNQ compound is substituted
or unsubstituted TCNQ and a compound obtained by substituting a
benzene ring portion of TCNQ with another aromatic ring or hetero
ring and examples thereof include TCNQ, TCAQ, or TCN3T. Further,
graphene may be exemplified. Particularly preferred examples of the
n-type organic semiconductor materials are described below.
R in the formula is not particularly limited, and preferred
examples thereof include a hydrogen atom, a substituted or
unsubstituted branched or linear alkyl group (having preferably 1
to 18 carbon atoms, more preferably 1 to 12 carbon atoms, and still
more preferably 1 to 8 carbon atoms), and a substituted or
unsubstituted aryl group (having preferably 6 to 30 carbon atoms,
more preferably 6 to 20 carbon atoms, and still more preferably 6
to 14 carbon atoms).
##STR00008## ##STR00009## ##STR00010## ##STR00011##
The above-described materials are used for film formation typically
by being mixed with a solvent, being applied to have a layer form,
and then being dried. As an application method, description of a
water-soluble resin film described below can be referred to.
Examples of the solvent include a hydrocarbon-based solvent such as
hexane, octane, decane, toluene, xylene, ethylbenzene,
1-methylnaphthalene, or 1,2-dichlorobenzene; a ketone-based solvent
such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or
cyclohexanone; a halogenated hydrocarbon-based solvent such as
dichloromethane, chloroform, tetrachloromethane, dichloroethane,
trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene,
or chlorotoluene; an ester-based solvent such as ethyl acetate,
butyl acetate, or amyl acetate; an alcohol-based solvent such as
methanol, propanol, butanol, pentanol, hexanol, cyclohexanol,
methyl cellosolve, ethyl cellosolve, or ethylene glycol; an
ether-based solvent such as dibutyl ether, tetrahydrofuran,
dioxane, or anisole; and a polar solvent such as
N,N-dimethylformamide, N,N-dimethylacetamide,
1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, or dimethyl
sulfoxide. These solvents may be used alone or in combination of
two or more kinds thereof.
The proportion of the organic semiconductor in a composition
(composition for forming an organic semiconductor) that forms the
organic semiconductor film is preferably in a range of 0.1% by mass
to 80% by mass and more preferably in a range of 0.1% by mass to
10% by mass, and a film having an arbitrary thickness can be formed
using the composition.
Further, a resin binder may be mixed with the composition for
forming an organic semiconductor. In this case, a material that
forms a film and a binder resin are dissolved in the
above-described suitable solvent or dispersed therein to make a
coating solution, and then a thin film can be formed using various
coating methods. Examples of the resin binder include an insulating
polymer such as polystyrene, polycarbonate, polyarylene, polyester,
polyamide, polyimide, polyurethane, polysiloxane, polysulfone,
polymethyl methacrylate, polymethyl acrylate, cellulose,
polyethylene, or polypropylene and a copolymer of these; a
photoconductive polymer such as polyvinyl carbazole or polysilane;
and a conductive polymer such as polythiophene, polypyrrole,
polyaniline, or polyparaphenylene vinylene. These resin binders may
be used alone or in combination of two or more kinds thereof. When
mechanical strength of a thin film is considered, a resin binder
having a high glass transition temperature is preferable. Further,
when charge mobility is considered, a resin binder having a
structure not containing a polar group, a photoconductive polymer,
or a conductive polymer is preferable.
In a case where a resin binder is to be mixed in, the amount to be
mixed in is preferably in a range of 0.1% by mass to 30% by mass in
a film such as an organic semiconductor film.
According to the application thereof, a mixed solution to which a
single or various semiconductor materials or additives are added
may be applied to form a film blend formed of a plurality of
materials. For example, in a case where a photoelectric conversion
layer is prepared, a solution into which another semiconductor
material is mixed can be used.
Moreover, at the time of film formation, a substrate may be heated
or cooled, and the film quality or packing of molecules in the film
can be controlled by changing the temperature of the substrate. The
temperature of the substrate, which is not particularly limited, is
preferably in a range of -200.degree. C. to 400.degree. C., more
preferably in a range of -100.degree. C. to 300.degree. C., and
still more preferably in a range of 0.degree. C. to 200.degree.
C.
The characteristics of the formed organic semiconductor film can be
adjusted by carrying out a post-treatment. For example, the
characteristics can be improved by changing a morphology of the
film or a packing of molecules of the film through exposure to a
heat treatment or solvent vapor. In addition, when the film is
exposed to a gas, a solvent, or a material having oxidizability or
reducibility or an oxidation or a reduction reaction is caused due
to these being mixed in, and the carrier density can then be
adjusted.
The film thickness of the organic semiconductor film is not
particularly limited and varies depending on the kind of an
electronic device to be used. The film thickness thereof is
preferably in a range of 5 nm to 50 .mu.m, more preferably in a
range of 10 nm to 5 .mu.m, and still more preferably in a range of
20 nm to 500 nm.
<<Water-Soluble Resin Film>>
The water-soluble resin film is formed by applying a water-soluble
resin composition containing a water-soluble resin to an organic
semiconductor film and drying the organic semiconductor film. The
water-soluble resin in the present invention indicates a resin
whose solubility in water at 20.degree. C. is 1% or greater.
The water-soluble resin film is unlikely to dissolve in a developer
containing an organic solvent and needs to be dissolved in water.
For this reason, the sp value (solubility parameter) of the
water-soluble resin of the water-soluble resin film is preferably
18 (MPa).sup.1/2 to less than 29 (MPa).sup.1/2, more preferably
18.5 (MPa).sup.1/2 to less than 29 (MPa).sup.1/2, still more
preferably 19 (MPa).sup.1/2 to less than 28 (MPa).sup.1/2, even
sill more preferably 19.5 (MPa).sup.1/2 to 27 (MPa).sup.1/2, and
particularly preferably 20 (MPa).sup.1/2 to 26 (MPa).sup.1/2. The
sp value is a value calculated by a Hoy method and the Hoy method
is described in "POLYMER HANDBOOK FOURTH EDITION".
Further, the water-soluble resin composition may contain two or
more kinds of water-soluble resin. In this case, it is preferable
that each of the two or more kinds of water-soluble resin are in
the above-described ranges.
Examples of the water-soluble resin used in the present invention
include polyvinylpyrrolidone, water-soluble polysaccharides
(water-soluble cellulose, methyl cellulose, hydroxyethyl cellulose,
hydroxypropyl cellulose, hydroxyethyl methyl cellulose, or
hydroxypropyl methyl cellulose), pullulan or a pullulan derivative,
starch, hydroxypropyl starch, carboxymethyl starch, chitosan, and
cyclodextrin), polyvinyl alcohol, polyethylene oxide, and polyethyl
oxazoline. Among these, polyvinylpyrrolidone, polyvinyl alcohol, or
pullulan is preferable. It is preferable that the water-soluble
resin includes polyvinylpyrrolidone, polyvinyl alcohol, or a
mixture of polyvinylpyrrolidone and polyvinyl alcohol.
In addition, two or more kinds having main chain-like structures
different from each other may be selected from among these and then
used or used as a copolymer.
In a case where polyvinyl alcohol is used as a water-soluble resin,
the saponification degree is preferably in a range of 70% by mole
to 95% by mole and more preferably in a range of 80% by mole to 90%
by mole.
The weight average molecular weight of the water-soluble resin that
forms the water-soluble resin film used in the present invention is
preferably in a range of 500 to 1,000,000, more preferably 2,000 to
800,000, and still more preferably 3,000 to 700,000 in terms of
polystyrene according to the GPC method.
The weight average molecular weight can be suitably selected
according to a substrate on which processing is performed. When the
weight average molecular weight is in the above-described range,
conformability with respect to an organic semiconductor substrate
with differences in level can be further improved and occurrence of
cracks on a film surface can be further minimized.
In addition, two or more water-soluble resins whose weight average
molecular weights are different from each other may be selected and
then used.
A water-soluble resin having a degree of dispersion (molecular
weight distribution) of typically in a range of 1.0 to 3.0 and
preferably in a range of 1.0 to 2.6 is preferably used.
It is preferable that the water-soluble resin composition that
forms the water-soluble resin film used in the present invention
contains a solvent.
In the water-soluble resin composition, it is preferable that
arbitrary components of a water-soluble resin and various additives
are dissolved in a solvent and that a solution is prepared.
As the solvent to be used for the water-soluble resin composition,
known solvents other than water can be used and alcohols can be
exemplified.
Examples of the solvent which are used for the water-soluble resin
composition include (1) primary alcohols such as methanol, ethanol,
1-propanol, 1-butanol, 1-pentanol, 3-methyl-1-butanol, 1-hexanone,
4-methyl-1-pentanol, 1-heptanol, 5-methyl-1-hexanol, 1-octanol,
6-methyl-1-heptanol, 1-nonanone, and 1-decanol; (2) secondary
alcohols such as 2-propanol, 2-butanol, 2-pentanol, 2-hexanol,
2-heptanol, 2-octanol, 2-nonanol, and 2-decanol; (3) tertiary
alcohols such as t-butanol, t-amyl alcohol, 2,3-dimethyl-2-butanol,
2-methyl-2-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol,
3-ethyl-2-methyl-3-pentanol, 2,3-dimethyl-2-pentanol,
2,3-dimethyl-3-pentanol, 2,3,4-trimethyl-3-pentanol, and
3,4,4-trimethyl-3-pentanol; (4) ethylene glycol monoalkyl ethers
such as ethylene glycol monomethyl ether, ethylene glycol monoethyl
ether, ethylene glycol monopropyl ether, and ethylene glycol
monobutyl ether; and (5) propylene glycol monoalkyl ethers such as
propylene glycol monomethyl ether, propylene glycol monoethyl
ether, propylene glycol monopropyl ether, and propylene glycol
monobutyl ether.
Among the above-described solvents, at least one from among water,
primary alcohols, and secondary alcohols is preferable and at least
one of water and 2-propanol is more preferable.
The solvent can be used alone or in a mixture of two or more kinds
thereof.
As a method of applying the water-soluble resin composition,
coating is preferable. Examples of the application method include a
casting method, a blade coating method, a wire bar coating method,
a spray coating method, a dipping (immersion) coating method, a
bead coating method, an air knife coating method, a curtain coating
method, an ink-jet method, a spin coating method, and a
Langmuir-Blodgett (LB) method. In the present invention, a casting
method, a spin coating method, or an ink-jet method is more
preferable. When such a process is carried out, it is possible to
produce a film such as an organic semiconductor film whose surface
is flat and which has a large area at a low cost.
The solid content concentration of the water-soluble resin
composition is preferably in a range of 0.5% by mass to 45% by
mass, more preferably in a range of 1.0% by mass to 40% by mass,
and still more preferably in a range of 2.0% by mass to 35% by
mass. When the solid content concentration is adjusted to be in the
above-described range, the composition can be uniformly
applied.
It is preferable that the water-soluble resin composition contains
a surfactant for the purpose of further improving coating
properties.
Any of a non-ionic surfactant, an anionic surfactant, and an
amphoteric fluorine-based surfactant may be used as a surfactant as
long as surface tension can be decreased. Examples of the
surfactant include non-ionic surfactants, for example,
polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether,
polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether;
polyoxyethylene alkyl allyl ethers such as polyoxyethylene
octylphenyl ether and polyoxyethylene nonylphenyl ether;
polyoxyethylene alkyl esters such as polyoxyethylene stearate;
sorbitan alkyl esters such as sorbitan monolaurate, sorbitan
monostearate, sorbitan distearate, sorbitan monooleate, sorbitan
sesquioleate, and sorbitan trioleate; monoglyceride alkyl esters
such as glycerol monostearate and glycerol monooleate; an oligomer
containing fluorine or silicon; acetylene glycol; and an ethylene
oxide adduct of acetylene glycol; anionic surfactants, for example,
alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate;
alkylnaphthalene sulfonates such as sodium butylnaphthalene
sulfonate, sodium pentylnaphthalene sulfonate, sodium
hexylnaphthalene sulfonate, and sodium octylnaphthalene sulfonate;
alkyl sulfates such as sodium lauryl sulfate; alkyl sulfonates such
as sodium dodecyl sulfonate; and sulfosuccinates such as sodium
dilauryl sulfosuccinate; and amphoteric surfactants, for example,
alkyl betaines such as lauryl betaine and stearyl betaine; and
amino acids. A non-ionic surfactant which has a small content of
metal ions affecting electrical characteristics of an organic
semiconductor, has excellent defoaming properties, and has an
acetylene skeleton represented by the following Formula (1) is
particularly preferable. R.sup.1--C.ident.C--R.sup.2 (1)
In Formula (1), R.sup.1 and R.sup.2 each independently represent an
alkyl group which may include a substituent and has 3 to 15 carbon
atoms, an aromatic hydrocarbon group which may include a
substituent and has 6 to 15 carbon atoms, or a heterocyclic
aromatic group which may include a substituent and has 4 to 15
carbon atoms (examples of the substituent include an alkyl group
having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6
to 15 carbon atoms, an aralkyl group having 7 to 17 carbon atoms,
an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl
group having 2 to 20 carbon atoms, or an acyl group having 2 to 15
carbon atoms).
In a case where the water-soluble resin composition contains a
surfactant, the amount of the surfactant to be added is preferably
in a range of 0.05% by mass to 8% by mass, more preferably in a
range of 0.07% by mass to 5% by mass, and particularly preferably
in a range of 0.1% by mass to 3% by mass when a water-soluble resin
film is obtained.
These surfactants may be used alone or in combination of two or
more kinds thereof.
The water-soluble resin composition may contain a plasticizer used
to improve the mechanical strength of a film. Particularly, when a
plasticizer is mixed in a case where the water-soluble resin film
needs to have a film thickness of 2 .mu.m or greater, generation of
cracks can be more effectively prevented.
Examples of the plasticizer which can be used include polyethylene
oxide, polypropylene oxide, a glycol, propylene glycol,
polyethylene glycol, a polyvalent alcohol, glycerin, sorbitol, a
glycerol ester, glycerol triacetate, a fatty acid triglyceride, and
a combination of these. Particularly, glycerin having excellent
compatibility with a water-soluble resin is preferable.
The film thickness of the water-soluble resin film is preferably in
a range of 20 nm to 10 .mu.m and more preferably in a range of 100
nm to 5 .mu.m. The film thickness can be suitably selected
according to the film thickness of an organic semiconductor on
which processing is performed. The time for etching can be
shortened as the film thickness of the water-soluble resin film
becomes smaller, but the water-soluble resin film is lost before
etching of the organic semiconductor is completed in a case where
the film thickness of the organic semiconductor is large. For this
reason, the organic semiconductor cannot be satisfactorily
processed. The time for etching becomes longer as the film
thickness of the water-soluble resin becomes larger, but the
organic semiconductor can be satisfactorily processed even when the
film thickness of the organic semiconductor is large.
The above-described film thickness can be obtained by setting the
solid content concentration in the water-soluble resin composition
to be in an appropriate range for a suitable viscosity and
improving the coating properties and film forming properties.
<<Chemically Amplified Photosensitive Resin
Composition>>
The photosensitive resin composition used in the present invention
is a chemically amplified photosensitive resin composition. By
allowing the photosensitive resin composition to be a chemically
amplified type, long storage stability and fine pattern forming
properties can be achieved.
In the present invention, when the chemically amplified
photosensitive resin composition (hereinafter, also simply referred
to as a "photosensitive resin composition") is exposed to light
under the condition of 100 mJ/cm.sup.2 or greater at a wavelength
of 365 nm, the polarity thereof is changed. The chemically
amplified photosensitive resin composition becomes hardly soluble
in an organic solvent having an sp value of preferably less than 19
(MPa).sup.1/2, more preferably 18.5 (MPa).sup.1/2 or less, and
still more preferably 18.0 (MPa).sup.1/2 or less. In addition, it
is more preferable that the polarity thereof is changed as
described above by the photosensitive resin composition being
exposed to light under the condition of 100 mJ/cm.sup.2 to 200
mJ/cm.sup.2 at a wavelength of 365 nm.
Since a finer trench hole pattern can be formed and thus
particularly good effects can be obtained, it is preferable that
the photosensitive resin composition used in the present invention
is a negative type resist composition.
It is preferable that the photosensitive resin composition used in
the present invention contains at least a resin (hereinafter,
referred to as a "specific resin A") which can be developed by a
developer containing an organic solvent and a photoacid generator
(hereinafter, also referred to as a "specific photoacid generator")
which is decomposed in an amount of 80% by mole or greater when
exposed to light under the condition of 100 mJ/cm.sup.2 or greater
at a wavelength of 365 nm. With the photosensitive resin
composition in the present invention, generation of a residue at
the time of development is prevented and a resist film having a
surface with excellent smoothness can be formed.
Here, the "residue" in the present invention indicates a residue
existing on the peripheral edge of the end portion of a
pattern-like resist film when the pattern-like resist film is
formed using the photosensitive resin composition.
Specific Resin A
The specific resin A used in the present invention is a resin
component constituting the chemically amplified photosensitive
resin composition, is typically a resin that includes a repeating
unit containing a group dissociated by an acid, and may include
another repeating unit.
For example, it is preferable that the specific resin A includes an
acid decomposable repeating unit (repeating unit that includes a
group dissociated by an acid) and is a resin whose dissolution rate
in a developer containing an organic solvent is decreased by an
action of an acid.
In the present invention, it is preferable that the specific resin
A is a resin which becomes soluble in an organic solvent having an
sp value of 18.0 (MPa).sup.1/2 or less and which becomes hardly
soluble in an organic solvent having an sp value of 18.0
(MPa).sup.1/2 or less when a tetrahydrofuranyl group (hereinafter,
also referred to as a "specific acid decomposable group") in a
constituent unit represented by Formula (1) is decomposed or
dissociated.
Here, the expression "soluble in an organic solvent having an sp
value of 18.0 (MPa).sup.1/2 or less" in the present invention means
that the dissolution rate of a coating film (thickness: 1 .mu.m) of
the specific resin A, in butyl acetate at 23.degree. C., which is
formed by coating a substrate with a solution of the specific resin
A and heating the substrate at 100.degree. C. for 1 minute is 20
nm/sec or greater. In addition, the expression "hardly soluble in
an organic solvent having an sp value of 18.0 (MPa).sup.1/2 or
less" means that the dissolution rate of a coating film (thickness:
1 .mu.m) of the specific resin A, in butyl acetate at 23.degree.
C., which is formed by coating a substrate with a solution of the
specific resin A and heating the substrate at 100.degree. C. for 1
minute is less than 10 nm/sec.
The dissolution rate of the specific resin A in the present
invention in an inorganic solvent having an sp value of 18.0
(MPa).sup.1/2 or less is more preferably 40 nm/sec or greater. In
addition, when the specific acid decomposable group of the specific
resin A is decomposed, the dissolution rate thereof in an inorganic
solvent having an sp value of 18.0 (MPa).sup.1/2 or less is
preferably less than 1 nm/sec.
It is preferable that the specific resin A in the present invention
is an acrylic polymer.
The "acrylic polymer" in the present invention is an addition
polymerization type resin and is a polymer including a constituent
unit derived from (meth)acrylic acid and/or an ester thereof.
Further, the acrylic polymer may include a constituent unit other
than the constituent unit derived from (meth)acrylic acid and/or an
ester thereof, for example, a constituent unit derived from
styrenes or a constituent unit derived from a vinyl compound.
It is preferable that the specific resin A includes 50% by mole or
greater of the constituent unit derived from (meth)acrylic acid
and/or an ester thereof, and more preferable that the specific
resin A includes 80% by mole or greater of the constituent unit
with respect to the total constituent units in a polymer, and
particularly preferable that the specific resin A is a polymer
formed only of the constituent unit derived from (meth)acrylic acid
and/or an ester thereof.
In addition, "the constituent unit derived from (meth)acrylic acid
and/or an ester thereof" is also referred to as an "acrylic
constituent unit". Further, (meth)acrylic acid is a general term
for methacrylic acid and acrylic acid.
Repeating Unit (a1)
The specific resin A used in the present invention normally
includes a repeating unit (a1) containing a group dissociated by an
acid. As a preferred example of the group dissociated by an acid, a
group represented by the following Formula (1) is exemplified.
##STR00012##
In Formula (1), R.sup.1 and R.sup.2 each independently represent a
hydrogen atom or a linear, branched, or cyclic alkyl group which
may be substituted. At this time, a case where both of R.sup.1 and
R.sup.2 represent a hydrogen atom is excluded.
R.sup.3 represents a linear, branched, or cyclic alkyl group which
may be substituted or an aralkyl group which may be
substituted.
R.sup.1 and R.sup.3 may be linked to each other to form a cyclic
ether.
In Formula (1), the number of carbon atoms of a linear or branched
alkyl group as R.sup.1 or R.sup.2 is preferably in a range of 1 to
6. As a substituent, an alkoxy group having 1 to 6 carbon atoms or
a halogen atom is preferable.
The number of carbon atoms of a cyclic alkyl group as R.sup.1 or
R.sup.2 is preferably in a range of 3 to 6. As a substituent, an
alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to
6 carbon atoms, or a halogen atom is preferable.
The number of carbon atoms of a linear or branched alkyl group as
R.sup.3 is preferably in a range of 1 to 10. As a substituent, an
alkoxy group having 1 to 6 carbon atoms or a halogen atom is
preferable.
The number of carbon atoms of a cyclic alkyl group as R.sup.3 is
preferably in a range of 3 to 10. As a substituent, an alkyl group
having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon
atoms, or a halogen atom is preferable.
The number of carbon atoms of an aralkyl group as R.sup.3 is
preferably in a range of 7 to 10. As a substituent, an alkyl group
having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon
atoms, or a halogen atom is preferable.
In the case where R.sup.1 and R.sup.3 are linked to each other to
form a cyclic ether, it is preferable that an alkylene chain having
2 to 5 carbon atoms is formed by R.sup.1 and R.sup.3 being linked
to each other.
As a constituent unit having an acid dissociable group represented
by Formula (1), a constituent unit in which a phenolic hydroxyl
group of hydroxystyrene or novolac is protected by an acetal group
is exemplified. As one of preferred constituent units, a
constituent unit having an acid dissociable group represented by
the following Formula (2) is exemplified, and examples thereof
include 1-alkoxyalkoxystyrene, 1-(haloalkoxy)alkoxystyrene,
1-(aralkyloxy)alkoxystyrene, and tetrahydropyranyloxystyrene. Among
these, 1-alkoxyalkoxystyrene or tetrahydropyranyloxystyrene is more
preferable and 1-alkoxyalkoxystyrene is particularly
preferable.
##STR00013##
In Formula (2), R.sup.1 and R.sup.2 each independently represent a
hydrogen atom or a linear, branched, or cyclic alkyl group which
may be substituted. At this time, a case where both of R.sup.1 and
R.sup.2 represent a hydrogen atom is excluded.
R.sup.3 represents a linear, branched, or cyclic alkyl group which
may be substituted or an aralkyl group which may be
substituted.
R.sup.1 and R.sup.3 may be linked to each other to form a cyclic
ether.
R.sup.4 represents a hydrogen atom or a methyl group.
In Formula (2), R.sup.1 to R.sup.3 have the same definitions as
those for R.sup.1 to R.sup.3 in Formula (1).
A constituent unit represented by Formula (2) may include a
substituent such as an alkyl group or an alkoxy group on a benzene
ring.
As another preferred example of a constituent unit having an acid
dissociable group represented by Formula (1), a repeating unit
represented by the following Formula (1-1) is exemplified.
##STR00014##
In Formula (1-1), R.sup.1 represents an alkyl group, R.sup.2
represents an alkyl group, and R.sup.3 represents a hydrogen atom
or an alkyl group. R.sup.1 and R.sup.2 may be linked to each other
to form a ring.
Ra represents a hydrogen atom, an alkyl group, a cyano group, or a
halogen atom.
L.sup.1 represents a single bond or a divalent linking group.
In Formula (1-1), an alkyl group as R.sup.1 may be linear,
branched, or cyclic. The linear or branched alkyl group may include
a substituent, and the number of carbon atoms thereof is preferably
in a range of 1 to 20 and more preferably in a range of 1 to 10.
Specific examples of the linear or branched alkyl group as R.sup.1
include a methyl group, an ethyl group, a propyl group, an
isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl
group, a neopentyl group, a hexyl group, a 2-ethylhexyl group, an
octyl group, and a dodecyl group. It is preferable that the alkyl
group as R.sup.1 is a methyl group, an ethyl group, a propyl group,
an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl
group, or a neopentyl group.
In Formula (1-1), the cyclic alkyl group as R.sup.1 may include a
substituent and may be a monocyclic type group or a polycyclic type
group. The number of carbon atoms thereof is preferably in a range
of 3 to 20 and more preferably in a range of 3 to 10. Specific
examples of the cyclic alkyl group as R.sup.1 include a cyclopropyl
group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group,
a cyloheptyl group, a cyclooctyl group, a decahydronaphthyl group,
a cyclodecyl group, a 1-adamantyl group, a 2-adamantyl group, a
1-norbornyl group, and a 2-norbornyl group. Among these, a
cyclopropyl group, a cyclopentyl group, a cyclohexyl group, or a
1-adamantyl group is preferable.
As a substituent which can be included in the linear or branched
alkyl group as R.sup.1, a cyclic alkyl group, an aryl group, an
alkoxy group, an aryloxy group, an acyl group, or a halogen atom
(for example, a fluorine atom or a chlorine atoms) is
exemplified.
Further, specific examples and preferred examples of the cyclic
alkyl group as a substituent which can be included in the linear or
branched alkyl group as R.sup.1 are the same as the specific
examples and preferred examples described above as the cyclic alkyl
group as R.sup.1.
Examples of the substituent which can be included in the cyclic
alkyl group as R.sup.1 include an alkyl group, an aryl group, an
alkoxy group, an aryloxy group, an acyl group, and a halogen
atom.
Specific examples and preferred examples of an alkyl group as the
substituent which can be included in the cyclic alkyl group as
R.sup.1 are the same as the specific examples and preferred
examples described above as the linear or branched alkyl group as
R.sup.1.
The aryl group as the substituent which can be included in the
alkyl group as R.sup.1 is preferably an aryl group having 6 to 15
carbon atoms and more preferably an aryl group having 6 to 12
carbon atoms, and has a structure (for example, a biphenyl group or
a terphenyl group) in which a plurality of aromatic rings are
connected to each other through a single bond. Specific examples of
the aryl group as the substituent which can be included in the
alkyl group as R.sup.1 include a phenyl group, a naphthyl group, an
anthranyl group, a biphenyl group, and a terphenyl group. Preferred
examples of the aryl group as the substituent which can be included
in the alkyl group as R.sup.1 include a phenyl group, a naphthyl
group, and a biphenyl group.
Examples of an alkyl group portion of the alkoxy group as the
substituent which can be included in the alkyl group as R.sup.1
include the same as those exemplified as the alkyl group of R.sup.1
in Formula (1-1). Particularly preferred examples of the alkoxy
group include a methoxy group, an ethoxy group, an n-propoxy group,
and an n-butoxy group.
Examples of an aryl group portion of the aryloxy group as the
substituent which can be included in the alkyl group as R.sup.1
include the same as those exemplified above as the aryl group.
Examples of an acyl group as the substituent which can be included
in the alkyl group or a cycloalkyl group as R.sup.1 include a
linear or branched acyl group having 2 to 12 carbon atoms such as
an acetyl group, a propionyl group, an n-butanoyl group, an
i-butanoyl group, an n-heptanoyl group, a 2-methylbutanoyl group, a
1-methylbutanoyl group, or a t-heptanoyl group.
In Formula (1-1), an alkyl group as R.sup.2 may be linear,
branched, or cyclic. The linear or branched alkyl group may include
a substituent, and the number of carbon atoms thereof is preferably
in a range of 1 to 30 and more preferably in a range of 1 to 20.
Specific examples of the linear or branched alkyl group as R.sup.2
include a methyl group, an ethyl group, a propyl group, an
isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl
group, a neopentyl group, a hexyl group, a 2-ethylhexyl group, an
octyl group, and a dodecyl group. It is preferable that the alkyl
group as R.sup.2 is a methyl group, an ethyl group, a propyl group,
an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl
group, or a neopentyl group.
The cyclic alkyl group as R.sup.2 may include a substituent and may
be a monocyclic type group or a polycyclic type group. The number
of carbon atoms thereof is preferably in a range of 3 to 30 and
more preferably in a range of 3 to 20. Specific examples of the
cyclic alkyl group as R.sup.2 include a cyclopropyl group, a
cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a
cyloheptyl group, a cyclooctyl group, a 1-adamantyl group, a
2-adamantyl group, a 1-norbornyl group, a 2-norbornyl group, a
bornyl group, an isobornyl group, a
4-tetracyclo[6.2.1.1.sup.3,6.0.sup.2,7]dodecyl group, an
8-tricyclo[5.2.1.0.sup.2,6]decyl group, and a 2-bicylo[2.2.1]heptyl
group. Among these, a cyclopentyl group, a cyclohexyl group, a
2-adamantyl group, an 8-tricyclo[5.2.1.0.sup.2,6]decyl group, and a
2-bicylo[2.2.1]heptyl group are preferable.
As a substituent which can be included in the linear or branched
alkyl group as R.sup.2, a cyclic alkyl group, an aryl group, a
heterocyclic group, an alkoxy group, an aryloxy group, an acyloxy
group, or a halogen atom (for example, a fluorine atom or a
chlorine atoms) is exemplified.
Further, specific examples and preferred examples of the cyclic
alkyl group as a substituent which can be included in the linear or
branched alkyl group as R.sup.2 are the same as the specific
examples and preferred examples described above as the cyclic alkyl
group as R.sup.2.
Examples of the substituent which can be included in the cyclic
alkyl group as R.sup.2 include an alkyl group, an aryl group, a
heterocyclic group, an alkoxy group, an aryloxy group, an acyloxy
group, and a halogen atom (for example, a fluorine atom or a
chlorine atom).
Specific examples and preferred examples of an alkyl group as the
substituent which can be included in the cyclic alkyl group as
R.sup.2 are the same as the specific examples and preferred
examples described above as the alkyl group as R.sup.1.
Examples of the aryl group as the substituent which can be included
in the alkyl group as R.sup.2 include the same as those exemplified
above as the substituent which can be included in the alkyl group
as R.sup.1.
The heterocyclic group as R.sup.2 is preferably a heterocyclic
group having 6 to 20 carbon atoms and more preferably a
heterocyclic group having 6 to 12 carbon atoms. Specific examples
of the heterocyclic ring as R.sup.2 include a pyridyl group, a
pyrazyl group, a tetrahydrofuranyl group, a tetrahydropyranyl
group, a tetrahydrothiophene group, a pyperidyl group, a piperazyl
group, a furanyl group, a pyranyl group, and a chromanyl group.
Examples of an alkyl group portion of the alkoxy group as the
substituent which can be included in the alkyl group as R.sup.2
include as those exemplified as the alkyl group as R.sup.1. As the
alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group,
or an n-butoxy group is particularly preferable.
Examples of an aryl group portion of the aryloxy group as the
substituent which can be included in the alkyl group as R.sup.2
include as those exemplified as the aryl group described above.
Examples of the acyloxy group as the substituent which can be
included in the alkyl group as R.sup.2 include a linear or branched
acyloxy group having 2 to 12 carbon atoms such as an acetyloxy
group, a propionyloxy group, an n-butanoyloxy group, an
i-butanoyloxy group, an n-heptanoyloxy group, a 2-methylbutanoyloxy
group, a 1-methylbutanoyloxy group, or a t-heptanoyloxy group.
In Formula (1-1), R.sup.1 and R.sup.2 may be linked to each other
to form a ring. The formed ring may include a substituent. It is
preferable that a 5- or 6-membered ring is formed and more
preferable that a tetrahydrofuranyl ring or a tetrahydropyranyl
group is formed.
In Formula (1-1), the number of carbon atoms of an alkyl group as
R.sup.3 is preferably in a range of 1 to 10, more preferably in a
range of 1 to 5, still more preferably in a range of 1 to 3, and
still more preferably 1 or 2 (that is, a methyl group or an ethyl
group). Specific examples of the alkyl group include a methyl
group, an ethyl group, an n-propyl group, an isopropyl group, an
n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl
group.
It is preferable that R.sup.3 represents a hydrogen atom or an
alkyl group having 1 to 5 carbon atoms, more preferable that
R.sup.3 represents a hydrogen atom or an alkyl group having 1 to 3
carbon atoms, still more preferable that R.sup.3 represents a
hydrogen atom or a methyl group, and particularly preferable that
R.sup.3 represents a hydrogen atom.
The alkyl group as Ra may include a substituent and is preferably
an alkyl group having 1 to 4 carbon atoms.
Preferred examples of the substituent which may be included in the
alkyl group as Ra include a hydroxyl group and a halogen atom.
Examples of the halogen atom as Ra include a fluorine atom, a
chlorine atom, a bromine atom, and an iodine atom.
As Ra, a methyl group, a hydroxymethyl group, or a perfluoroalkyl
group having 1 to 4 carbon atoms (for example, a trifluoromethyl
group) is preferable and a methyl group is particularly preferable
from viewpoints of improving a glass transition point (Tg) of a
specific resin (A) and improving resolving power and space width
roughness.
At this time, in a case where L.sup.1 represents a phenylene group,
it is preferable that Ra represents a hydrogen atom.
As the divalent linking group as L.sup.1, an alkylene group, a
divalent aromatic ring group, --COO-L.sup.11-, --O-L.sup.11-, or a
group obtained by combining two or more of these is exemplified.
Here, L.sup.11 represents an alkylene group, a divalent aromatic
ring group, or a group obtained by combining an alkylene group and
a divalent aromatic ring group.
As the divalent aromatic ring group, a phenylene group such as a
1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene
group; or a 1,4-naphthylene group is preferable and a 1,4-phenylene
group is more preferable.
It is preferable that L.sup.1 represents a single bond, a group
represented by --COO-L.sup.a-, or a group represented by
-L.sup.12-O--CH.sub.2-- and particularly preferable that L.sub.1
represents a single bond. Here, L.sup.12 represents a divalent
aromatic ring group.
In a case where the alkylene group as L.sup.11 is a cyclic alkylene
group, the alkylene group contains an ester bond and may form a
lactone ring. It is preferable that L.sup.11 represents an alkylene
group which has 1 to 9 carbon atoms and may contain a heteroatom or
a carbonyl bond and more preferable that L.sup.11 represents a
methylene group, an ethylene group, or a propylene group.
It is preferable that L.sup.12 represents an arylene group having 1
to 10 carbon atoms, more preferable that L.sup.12 represents a
1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene
group, and still more preferable that L.sup.12 represents a
1,4-phenylene group or a 1,3-phenylene group.
Preferred specific examples of the divalent linking group as
L.sup.1 are shown below, but the present invention is not limited
thereto.
##STR00015##
From a viewpoint that the glass transition point (Tg) of the
specific resin (A) is further increased and thus the resolving
power or the like can be further improved when a fine pattern is
formed, it is preferable that the repeating unit represented by
Formula (1-1) is a repeating unit represented by the following
Formula (1-11).
##STR00016##
In Formula (1-11), R.sup.2, R.sup.3, L.sup.1, and Ra have the same
definitions as those for R.sup.2, R.sup.3, L.sup.1, and Ra in
Formula (1-1).
R.sup.11 represents an alkyl group, an aryl group, an aralkyl
group, an alkoxy group, an acyl group, or a heterocyclic group.
R.sup.11 and R.sup.2 may be linked to each other to form a
ring.
R.sup.11 may represent a linear, branched, or cyclic alkyl
group.
Specific examples and preferred examples of the alkyl group as
R.sup.11 are the same as those described above as the specific
examples and preferred examples of the alkyl group as R.sup.1.
Specific examples and preferred examples of the aryl group as
R.sup.11 are the same as those described above as a substituent
which can be included in the alkyl group as R.sup.1.
It is preferable that the aralkyl group as R.sup.11 is an aralkyl
group having 6 to 20 carbon atoms and more preferable that the
aralkyl group as R.sup.11 is an aralkyl group having 7 to 12 carbon
atoms. Specific examples of the aralkyl group as R.sup.11 include a
benzyl group, a phenethyl group, a naphthylmethyl group, and a
naphthylethyl group.
Examples of an alkyl group portion of the alkoxy group as R.sup.11
include those exemplified as the alkyl group as R.sup.1. As the
alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group,
or an n-butoxy group is particularly preferable.
Examples of the acyl group as R.sup.11 include a linear or branched
acyl group having 2 to 12 carbon atoms such as acetyl group, a
propionyl group, an n-butanoyl group, an i-butanoyl group, an
n-heptanoyl group, a 2-methylbutanoyl group, a 1-methylbutanoyl
group, or a t-heptanoyl group.
The heterocyclic group as R.sup.11 is preferably a heterocyclic
group having 6 to 20 carbon atoms and more preferably a
heterocyclic group having 6 to 12 carbon atoms. Specific examples
of the heterocyclic ring as R.sup.11 include a pyridyl group, a
pyrazyl group, a tetrahydrofuranyl group, a tetrahydropyranyl
group, a tetrahydrothiophene group, a pyperidyl group, a piperazyl
group, a furanyl group, a pyranyl group, and a chromanyl group.
R.sup.11 and R.sup.2 may be linked to each other to form a ring.
The formed ring may include a substituent. It is preferable that a
5- or 6-membered ring is formed and more preferable that a
tetrahydrofuranyl ring or a tetrahydropyranyl group is formed.
The alkyl group, the aryl group, the aralkyl group, the alkoxy
group, the acyl group, and the heterocyclic group as R.sup.11 may
further include a substituent.
Examples of the substituent which can be further included in the
alkyl group as R.sup.11 include a cyclic alkyl group, an aryl
group, an amino group, an amide group, an ureido group, an urethane
group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy
group, an aralkyloxy group, a thioether group, an acyl group, an
acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro
group.
In addition, the number of carbon atoms of the alkyl group and the
number of carbon atoms of the substituent which can be further
included in the cyclic alkyl group are respectively and preferably
in a range of 1 to 8.
Examples of a substituent which can be further included in the aryl
group, the aralkyl group, the heterocyclic ring, and a ring formed
by R.sup.11 and R.sup.2 being linked to each other as R.sup.11
include a nitro group, a halogen atom such as a fluorine atom, a
carboxyl group, a hydroxyl group, an amino group, a cyano group, an
alkyl group (preferably having 1 to 15 carbon atoms), an alkoxy
group (preferably having 1 to 15 carbon atoms), a cycloalkyl group
(preferably having 3 to 15 carbon atoms), an aryl group (preferably
having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably
having 2 to 7 carbon atoms), an acyl group (preferably having 2 to
12 carbon atoms), and an alkoxycarbonyloxy group (preferably having
2 to 7 carbon atoms).
From a viewpoint that the glass transition point (Tg) of the
specific resin (A) is further increased and thus the resolving
power or the like can be further improved when a fine pattern is
formed, it is preferable that the repeating unit represented by
Formula (1-11) is a repeating unit represented by the following
Formula (1-12).
##STR00017##
In Formula (1-12) above, R.sup.2, R.sup.3, L.sup.1, and Ra have the
same definitions as those for R.sup.2, R.sup.3, L.sup.1, and Ra in
Formula (1-1).
R.sup.21 to R.sup.23 each independently represent a hydrogen atom,
an alkyl group, an aryl group, an aralkyl group, or a heterocyclic
group, and at least two of R.sup.21 to R.sup.23 each independently
represent an alkyl group, an aryl group, an aralkyl group, or a
heterocyclic group.
At least two or R.sup.21 to R.sup.23 may be bonded to each other to
form a ring. At least one of R.sup.21 to R.sup.23 may be bonded to
R.sup.2 to form a ring.
The alkyl group as R.sup.21 to R.sup.23 may be linear, branched, or
cyclic. Specific examples and preferred examples of the alkyl group
as R.sup.21 to R.sup.23 are the same as those described above as
the specific examples and preferred examples of the alkyl group as
R.sup.1.
As described above, it is preferable that at least two of R.sup.21
to R.sup.23 each independently represent an alkyl group, an aryl
group, an aralkyl group, or a heterocyclic ring and all of R.sup.21
to R.sup.23 represent an alkyl group, an aryl group, an aralkyl
group, or a heterocyclic ring.
Specific examples and preferred examples of the cyclic alkyl group
as R.sup.21 to R.sup.23 are the same as those described above as
the specific examples and preferred examples of the cyclic alkyl
group as R.sup.1.
Specific examples and preferred examples of the cyclic aryl group
as R.sup.21 to R.sup.23 are the same as the aryl group described
above as a sub stituent which can be included in the alkyl group or
the cyclo alkyl group as R.sup.1.
Specific examples and preferred examples of the aralkyl group as
R.sup.21 to R.sup.23 are the same as those described above as the
specific examples and preferred examples of the aralkyl group as
R.sup.11.
Specific examples and preferred examples of the heterocyclic group
as R.sup.21 to R.sup.23 are the same as those described above as
the specific examples and preferred examples of the aralkyl group
as R.sup.11.
At least one of R.sup.21 to R.sup.23 may be linked to R.sup.2 to
form a ring. The formed ring may include a substituent. It is
preferable that a 5- or 6-membered ring is formed and more
preferable that a tetrahydrofuranyl ring or a tetrahydropyranyl
group is formed.
The alkyl group, the aryl group, the aralkyl group, and the
heterocyclic group as R.sup.21 to R.sup.23 may further include a
substituent.
Specific examples of the substituent which can be further included
in the alkyl group as R.sup.21 to R.sup.23 are the same those
described above as the specific examples of the substituent which
can be further included in the alkyl group as R.sup.11.
In addition, the number of carbon atoms of the alkyl group and the
number of carbon atoms of the substituent which can be further
included in the alkyl group are respectively and preferably in a
range of 1 to 8.
Specific examples and preferred examples of the substituent which
can be further included in the aryl group, the aralkyl group, or
the heterocyclic ring as R.sup.21 to R.sup.23, or the ring formed
by at least one of R.sup.21 to R.sup.23 being linked to R.sub.2 are
the same as those described above as the specific examples and
preferred examples of the substituent which can be further included
in the aryl group, the aralkyl group, or the heterocyclic ring as
R.sup.11, or the ring formed by R.sup.11 and R.sup.2 being linked
to each other.
At least two of R.sup.21 to R.sup.23 may be bonded to each other to
form a ring.
In a case where at least two of R.sup.21 to R.sup.23 are bonded to
each other to form a ring, examples of a ring which is formed
include a cyclopentane ring, a cyclohexane ring, an adamantane
ring, a norbornene ring, and a norbornane ring. Among these, a
cyclohexane ring is particularly preferable. These rings may
include a substituent and examples of the substituent which can be
included include respective groups described above as the specific
examples of the alkyl group and the substituent which can be
included in the alkyl group.
In a case where all of R.sup.21 to R.sup.23 are bonded to each
other to form a ring, examples of the ring to be formed include an
adamantane ring, a norbornane ring, a norbornene ring, a
bicylo[2,2,2]octane ring, and a bicylo[3,1,1]heptane ring. Among
these, an adamantane ring is particularly preferable. These rings
may include a substituent and examples of the substituent which can
be included include respective groups described above as the
specific examples of the alkyl group and the substituent which can
be included in the alkyl group.
From a viewpoint that the glass transition point of the specific
resin (A) is higher and the resolving power can be improved, it is
preferable that R.sup.21 to R.sup.23 each independently represent
an alkyl group.
The number of carbon atoms of a group represented by
--C(R.sup.21)(R.sup.22)(R.sup.23) in Formula (1-12) above is
preferably 15 or less. In this manner, the affinity between a
resist film to be obtained and a developer becomes sufficient and
an exposed portion can be more reliably removed by the developer
(that is, developability can be sufficiently obtained).
Specific examples of R.sup.11 (preferably, a group represented by
--C(R.sup.21)(R.sup.22)(R.sup.23)) will be shown below, but the
present invention is not limited thereto. In the specific examples
shown below, "*" represents a bond connected to a group represented
by --CH.sub.2-- of Formula (1-11) or (1-12).
##STR00018## ##STR00019## ##STR00020##
In the same manner, from a viewpoint that the glass transition
point (Tg) of the specific resin (A) is further increased and thus
the resolving power or the like can be further improved when a fine
pattern is formed, it is preferable that the repeating unit
represented by Formula (1-1) is a repeating unit represented by the
following Formula (1-13).
##STR00021##
In Formula (1-13) above, R.sup.2, R.sup.3, L.sup.1, and Ra have the
same definitions as those for R.sup.2, R.sup.3, L.sup.1, and Ra in
Formula (1-1).
R.sup.24 to R.sup.26 each independently represent an alkyl group,
an aryl group, an aralkyl group, or a heterocyclic group. Preferred
examples of R.sup.24 to R.sup.26 are the same as the preferred
examples described above as R.sup.21 to R.sup.23, but it is more
preferable that all of R.sup.24 to R.sup.26 represent an alkyl
group, still more preferable that all of R.sup.24 to R.sup.26
represent a linear or branched alkyl group, and particularly
preferable that all of R.sup.24 to R.sup.26 represent a methyl
group.
At least two of R.sup.24 to R.sup.26 may be bonded to each other to
form a ring. Preferred examples of the ring to be formed include
the examples described above in regard to a ring which is formed by
at least two of R.sup.21 to R.sup.23 being bonded to each other.
Particularly, preferred examples thereof include a cyclopentyl
ring, a cyclohexyl ring, a norbornene ring, and an adamantane
ring.
At least one of R.sup.24 to R.sup.26 may be bonded to R.sup.2 to
form a ring. Preferred examples of the ring to be formed include
the examples described above in regard to a ring formed by at least
one of R.sup.21 to R.sup.23 being bonded to R.sup.2.
From viewpoints of further reliably securing a high contrast
(.gamma. value is high), improving resolving power and space width
roughness in formation of a fine isolated space pattern, and more
reliably achieving high resolving power, excellent exposure
latitude, and uniformity of local pattern dimensions in formation
of a fine hole pattern, the content of a repeating unit (total
content in a case where plural kinds of repeating unit are
included) represented by Formula (1-1), (1-11), or (1-12) in the
specific resin (A) is preferably 55% by mole or greater and more
preferably 60% by mole or greater with respect to all repeating
units in the specific resin (A).
The upper limit thereof, which is not particularly limited, is
preferably 85% by mole or less, more preferably 80% by mole or
less, and still more preferably 75% by mole or less from a
viewpoint of more reliably achieving the effects of the present
invention.
The copolymerization composition of the constituent units which
include an acid dissociable group represented by Formula (1) is
preferably in a range of 10% by mole to 90% by mole and more
preferably in a range of 20% by mole to 50% by mole with respect to
all components.
It is more preferable that the specific resin A includes a
repeating unit containing a cyclic ether ester group as a group
dissociated by an acid. As the repeating unit containing a cyclic
ether ester group, a repeating unit represented by the following
Formula (11) is more preferable.
##STR00022##
(In Formula (11), R.sup.1 represents a hydrogen atom or an alkyl
group, L.sup.1 represents a carbonyl group or a phenylene group,
R.sup.21 to R.sup.27 each independently represent a hydrogen atom
or an alkyl group.)
Next, the constituent unit represented by Formula (11) will be
described in detail.
Examples of the alkyl group as R.sup.1 include a linear, branched,
or cyclic alkyl group having 1 to 20 carbon atoms and specific
examples thereof include a methyl group, an ethyl group, a propyl
group, a butyl group, a pentyl group, a hexyl group, a heptyl
group, an octyl group, a nonyl group, a decyl group, an undecyl
group, a dodecyl group, a tridecyl group, a hexadecyl group, an
octadecyl group, an eicosyl group, an isopropyl group, an isobutyl
group, an s-butyl group, a t-butyl group, an isopentyl group, a
neopentyl group, a 1-methylbutyl group, an isohexyl group, a
2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a
cyclopentyl group, and a 2-norbornyl group. Among these alkyl
groups, a linear alkyl group having 1 to 12 carbon atoms, a
branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl
group having 5 to 10 carbon atoms is preferable, a linear alkyl
group having 1 to 12 carbon atoms is more preferable, and a methyl
group or an ethyl group is still more preferable.
Among these, it is preferable that R.sup.1 represents a hydrogen
atom or a methyl group and more preferable that R.sup.1 represents
a methyl group.
L.sup.1 represents a carbonyl group or a phenylene group and it is
preferable that L.sup.1 represents a carbonyl group.
R.sup.21 to R.sup.27 each independently represent a hydrogen atom
or an alkyl group. The alkyl group as R.sup.21 to R.sup.27 has the
same definition as that for R.sup.1 and the preferred embodiment is
the same as that of R.sup.1.
In addition, from viewpoints of decomposition properties and
synthesis, it is preferable that one or more of R.sup.21 to
R.sup.27 represent a hydrogen atom and more preferable that all of
R.sup.21 to R.sup.27 represent a hydrogen atom.
The constituent unit represented by Formula (11) in the present
invention contains a protected carboxy group and/or a protected
phenolic hydroxyl group.
A carboxylic acid monomer which is capable of forming a unit
represented by Formula (11) can be used as a constituent unit by a
carboxy group being protected if the carboxylic acid monomer may
become a constituent unit when the carboxy group is protected, and
examples thereof include acrylic acid and methacrylic acid. In
addition, as the constituent unit, a constituent unit derived from
carboxylic acid in which these carboxylic groups are protected is
preferably exemplified.
When the phenolic hydroxyl group is protected, as a monomer
including a phenolic hydroxyl group which is capable of forming a
constituent unit represented by Formula (11), a monomer which may
become a constituent unit by a phenolic hydroxyl group being
protected can be used. Preferred examples thereof include
hydroxystyrenes such as p-hydroxystyrene and
.alpha.-methyl-p-hydroxystyrene. Among these,
.alpha.-methyl-p-hydroxystyrene is more preferable.
As a radical polymerizable monomer used to form a constituent unit
represented by Formula (11), a commercially available product or a
product obtained through synthesis using a known method can be
used. For example, the radical polymerizable monomer can be
synthesized by reacting (meth)acrylic acid with a dihydrofuran
compound in the presence of an acid catalyst.
Further, after a carboxy group to be protected or a phenolic
hydroxyl group-containing monomer is polymerized with constituent
units (a2) to (a4) described below or a precursor thereof, the
radical polymerizable monomer can be formed by reacting a carboxy
group or a phenolic hydroxyl group with a dihydrofuran compound. In
addition, preferred specific examples of a constituent unit to be
formed in the above-described manner are the same as the
constituent units derived from the preferred specific examples of
the radical polymerizable monomer.
As a group which is included in the specific resin A and is
dissociated by an acid, a group represented by the following
Formula (B.sup.1) is preferably exemplified.
##STR00023##
In Formula (B.sup.1), the wavy line indicates a position linked to
a main chain or a side chain of the specific resin A.
R.sup.b11, R.sup.b12, and R.sup.b13 each independently represent a
group selected from an unsubstituted linear or branched alkyl group
having 1 to 20 carbon atoms or an unsubstituted cyclic alkyl group
having 3 to 20 carbon atoms, and two of R.sup.b11, R.sup.b12, and
R.sup.b13, may be bonded to each other to form a ring.
R.sup.b11, R.sup.b12, and R.sup.b13 each independently represent a
group selected from an unsubstituted linear or branched alkyl group
having 1 to 20 carbon atoms or an unsubstituted cyclic alkyl group
having 3 to 10 carbon atoms.
The number of carbon atoms of the unsubstituted linear alkyl group
is preferably in a range of 1 to 20, more preferably in a range of
1 to 15, and still more preferably in a range of 1 to 10. Specific
examples thereof include a methyl group, an ethyl group, a propyl
group, a hexyl group, and an octyl group.
The number of carbon atoms of the unsubstituted branched alkyl
group is preferably in a range of 3 to 20, more preferably in a
range of 3 to 15, and still more preferably in a range of 3 to 10.
Specific examples thereof include an iso-propyl group, an n-butyl
group, a sec-butyl group, a tert-butyl group, and an iso-butyl
group.
The number of carbon atoms of the unsubstituted cyclic alkyl group
is preferably in a range of 3 to 20, more preferably in a range of
3 to 15, and still more preferably in a range of 3 to 10. The
cyclic alkyl group may be monocyclic or polycyclic. Specific
examples thereof include a cyclopropyl group, a cyclobutyl group, a
cyclopentyl group, a cyclohexyl group, a norbornyl group, an
isobornyl group, a camphanyl group, an adamantyl group, a
dicyclopentyl group, an .alpha.-pinel group, and a tricyclodecanyl
group.
Two of R.sup.b11, R.sup.b12, and R.sup.b13 may be bonded to each
other to form a ring. Examples of a ring formed by two of
R.sup.b11, R.sup.b12 and R.sup.b13 being bonded to each other
include a cyclopentane ring, a cyclohexane ring, a norbornane ring,
an isobornane ring, and an adamantane ring.
As a repeating unit which contains a group represented by Formula
(B.sup.1), a repeating unit represented by the following Formula
(B.sup.1-1) is preferably exemplified.
##STR00024##
In Formula (B.sup.1-1), R.sup.1 represents a hydrogen atom, an
alkyl group, a cyano group, or a halogen atom. R.sup.2 to R.sup.4
each independently represent an alkyl group and two of R.sup.2 to
R.sup.4 may be bonded to each other to form a cyclic alkyl
group.
In Formula (B.sup.1-1), it is preferable that R.sup.1 represents a
hydrogen atom or an alkyl group.
In Formula (B.sup.1-1), in a case where R.sup.1 represents an alkyl
group, the definition of R.sup.1 is the same as that for R.sup.1 in
Formula (11) and the preferred ranges are the same as each
other.
In Formula (B.sup.1-1), in a case where R.sup.1 represents a
halogen atom, a fluorine atom, a chlorine atom, or a bromine atom
is preferable.
In Formula (B.sup.1-1), the definition of R.sup.2 is the same as
that for R.sup.b11 in Formula (B.sup.1) and a methyl group is
preferable.
In Formula (B.sup.1-1), the definition of R.sup.3 is the same as
that for R.sup.b12 in Formula (B.sup.1) and a methyl group is
preferable.
In Formula (B.sup.1-1), the definition of R.sup.4 is the same as
that for R.sup.b13 in Formula (B.sup.1) and a methyl group is
preferable.
In Formula (B.sup.1-1), in a case where two of R.sup.2 to R.sup.4
are bonded to each other to form a cyclic alkyl group, it is
preferable that R.sup.2 and R.sup.3 or R.sup.3 and R.sup.4 are
bonded to each other. The number of carbon atoms of the cyclic
alkyl group to be formed is preferably in a range of 3 to 10.
As a repeating unit which contains a group represented by Formula
(B.sup.1), a repeating unit represented by the following Formula
(B.sup.1-2) is also preferable.
##STR00025##
In Formula (B.sup.1-2), R.sup.1 represents a hydrogen atom, an
alkyl group, a cyano group, or a halogen atom. R.sup.2 to R.sup.4
each independently represent an alkyl group; and two of R.sup.2 to
R.sup.4 may be bonded to each other to form a cyclic alkyl group.
R.sup.5 represents a divalent chain-like hydrocarbon group.
In Formula (B.sup.1-2), it is preferable that R.sup.1 represents a
hydrogen atom or an alkyl group.
In Formula (B.sup.1-2), in a case where R.sup.1 represents an alkyl
group, the definition of R.sup.1 is the same as that for R.sup.1 in
Formula (11) and the preferred ranges are the same as each
other.
In Formula (B.sup.1-2), in a case where R.sup.1 represents a
halogen atom, the definition of R.sup.1 is the same as that for
R.sup.1 in Formula (B.sup.1-1), and the preferred ranges are the
same as each other.
In Formula (B.sup.1-2), the definitions of R.sup.2 to R.sup.4 are
the same as those for R.sup.2 to R.sup.4 in Formula (B.sup.1-1) and
a methyl group is preferable.
In Formula (B.sup.1-2), in a case where two of R.sup.2 to R.sup.4
are bonded to each other to form a cyclic alkyl group, it is
preferable that R.sup.2 and R.sup.3 or R.sup.3 and R.sup.4 are
bonded to each other. The number of carbon atoms of the cyclic
alkyl group to be formed is preferably in a range of 3 to 10.
In Formula (B.sup.1-2), R.sup.5 represents a divalent chain-like
hydrocarbon group. The chain-like hydrocarbon group may be a linear
or branched chain-like group and a linear chain-like group is
preferable. The number of carbon atoms of the chain-like
hydrocarbon group is preferably in a range of 1 to 10, more
preferably 1 to 6, and still more preferably in a range of 1 to 3.
Particularly, as the chain-like hydrocarbon group, an alkylene
group having 1 to 3 carbon atoms is preferable and a methylene
group is more preferable.
As a repeating unit which contains a group represented by Formula
(B.sup.1), a repeating unit represented by the following Formula
(IV) is also preferable.
##STR00026##
In Formula (IV), R.sup.42, R.sup.43, and R.sup.44 each
independently represent a group selected from an unsubstituted
linear or branched alkyl group having 1 to 20 carbon atoms or an
unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, and
R.sup.42, R.sup.43, and R.sup.44 may be bonded to one another to
form a ring. L.sup.4 represents a divalent linking group.
The definitions of R.sup.42, R.sup.43, and R.sup.44 are the same as
those for R.sup.2 to R.sup.4 in Formula (B.sup.1-1) and preferred
ranges are the same as each other.
L.sup.4 represents a divalent linking group. Examples of the
divalent linking group include a linear, branched, or cyclic
alkylene group and a group formed by combining these. These groups
may contain at least one selected from an ester bond, an ether
bond, an amide bond, and an urethane bond. Further, these groups
may be unsubstituted or may include a substituent. As the
substituent, a hydroxyl group or the like is exemplified. As the
substituent, it is preferable that a substituent other than a
hydroxyl group is not contained.
The number of carbon atoms of the linear alkylene group is
preferably in a range of 2 to 10.
The number of carbon atoms of the branched alkylene group is
preferably in a range of 3 to 10.
The number of carbon atoms of the cyclic alkylene group is
preferably in a range of 3 to 10.
Specific examples of the divalent linking group include an ethylene
group, a propylene group, a butylene group, a hexylene group, a
2-hydroxy-1,3-propanediyl group, a 3-oxa-1,5-pentanediyl group, and
a 3,5-dioxa-1,8-octanediyl group.
As another example of a group which is included in the specific
resin A and is dissociated by an acid, a group in which a hydrogen
atom of an alkali-soluble group (i) is substituted with an
acid-dissociable dissolution inhibition group (ii) represented by
the following Formula (21) is preferably exemplified.
--CH.sub.2--OCH.sub.2.sub.nR.sup.1 Formula (21)
(In the formula, R.sup.1 represents an aliphatic cyclic group
having 20 or less carbon atoms. n represents an integer of 0 or 1
to 5.)
It is preferable that the alkali-soluble group (i) is one or more
selected from an alcoholic hydroxyl group, a phenolic hydroxyl
group, and a carboxyl group. Among these, because of high
transparency and suitable alkali solubility, an alcoholic hydroxyl
group is preferable. Among these, it is more preferable that the
alcoholic hydroxyl group is an alcoholic hydroxyl group in which a
carbon atom adjacent to a carbon atom which is bonded to the
alcoholic hydroxyl group has at least one fluorine atom.
The alcoholic hydroxyl group may be simply a hydroxy group, or may
be an alcoholic hydroxyl group-containing alkyloxy group, an
alcoholic hydroxyl group-containing alkyloxyalkyl group, or an
alcoholic hydroxyl group-containing alkyl group. As the alkyloxy
group, the alkyloxyalkyl group, or the alkyl group, a lower
alkyloxy group, a lower alkyloxy lower alkyl group, or a lower
alkyl group is exemplified. The term "lower" here means that the
number of carbon atoms is 4 or less.
Specific examples of the lower alkyloxy group include a methyloxy
group, an ethyloxy group, a propyloxy group, and a butyloxy group.
Specific examples of the lower alkyloxy lower alkyl group include a
methyloxy methyl group, an ethyloxy methyl group, a propyloxy
methyl group, and a butyloxy methyl group. Specific examples of the
lower alkyl group include a methyl group, an ethyl group, a propyl
group, and a butyl group.
In addition, a part or all of hydrogen atoms of an alkyloxy group,
an alkyloxy alkyl group, or an alkyl group in an alcoholic hydroxyl
group-containing alkyloxy group, or an alcoholic hydroxyl
group-containing alkyl alkyl group, or an alcoholic hydroxyl
group-containing alkyl group may be substituted with fluorine
atoms. Preferred examples thereof include a group obtained by
substituting a part of hydrogen atoms of these alkyloxy portions in
an alcoholic hydroxyl group-containing alkyloxy group or an
alcoholic hydroxyl group-containing alkyloxyalkyl group with
fluorine atoms; and a group obtained by substituting a part of
hydrogen atoms of the alkyl group in an alcoholic hydroxyl
group-containing alkyl group with fluorine atoms, that is, an
alcoholic hydroxyl group-containing fluoroalkyloxy group, an
alcoholic hydroxyl group-containing fluoroalkyloxy alkyl group, or
an alcoholic hydroxyl group-containing fluoroalkyl group.
Examples of the alcoholic hydroxyl group-containing fluoroalkyloxy
group include a (HO)C(CF.sub.3).sub.2CH.sub.2O-group-containing
(2-bis(hexafluoromethyl)-2-hydroxy-ethyloxy group and a
(HO)C(CF.sub.3).sub.2CH.sub.2CH.sub.2O-group-containing
(3-bis(hexafluoromethyl)-3-hydroxy-propyloxy group. Examples of the
alcoholic hydroxyl group-containing fluoroalkyloxy alkyl group
include a (HO)C(CF.sub.3).sub.2CH.sub.2O--CH.sub.2-group and a
(HO)C(CF.sub.3).sub.2CH.sub.2CH.sub.2O--CH.sub.2-group. Examples of
the alcoholic hydroxyl group-containing fluoroalkyl group include a
(HO)C(CF.sub.3).sub.2CH.sub.2-group-containing
(2-bis(hexafluoromethyl)-2-hydroxy-ethyl group, and a
(HO)C(CF.sub.3).sub.2CH.sub.2CH.sub.2-group-containing
(3-bis(hexafluoromethyl)-3-hydroxy-propyl group.
As the phenolic hydroxyl group, a phenolic hydroxyl group contained
in a novolac resin or poly-(.alpha.-methyl)hydroxystyrene is
exemplified. Among these, from a viewpoint of availability at a low
cost, a phenolic hydroxyl group of
poly-(.alpha.-methyl)hydroxystyrene is preferable.
As the carboxyl group, a carboxyl group in a constituent unit
derived from an ethylenically unsaturated carboxylic acid is
exemplified. Examples of the ethylenically unsaturated carboxylic
acid include an unsaturated carboxylic acid such as acrylic acid,
methacrylic acid, maleic acid, or fumaric acid. Among these, from a
viewpoint of availability at a low cost, acrylic acid and
methacrylic acid are preferable.
In Formula (21), R.sup.1 represents an aliphatic cyclic group
having 20 or less carbon atoms, and an aliphatic cyclic group
having 5 to 12 carbon atoms is preferable. The aliphatic cyclic
group may include a substituent. The value of n is preferably 0 or
1.
The term "aliphatic cyclic group" indicates a monocyclic group or a
polycyclic group (alicyclic group) which is not aromatic. The
"aliphatic cyclic group" is not limited to a group formed of carbon
and hydrogen, but it is preferable that the aliphatic cyclic group
is a hydrocarbon group. In addition, the "hydrocarbon group" may be
saturated or unsaturated, but normally it is preferable that the
hydrocarbon group is saturated.
Examples of such an aliphatic cyclic group include a monovalent
group derived from cyclohexane, cyclopentane, adamantane,
norbornane, norbornene, methylnorbornane, ethylnorbornane,
methylnorbornene, ethylnorbornene, isobornane, tricyclodecane, or
tetracyclododecane. Such an aliphatic cyclic group can be used by
being appropriately selected from groups which have been suggested
multiple times in an ArF resist. Among these, a cyclohexyl group, a
cyclopentyl group, an adamantyl group, a norbornyl group, a
norbornenyl group, a methylnorbornyl group, an ethylnorbornyl
group, a methylnorbornenyl group, an ethylnorbornenyl group, or a
tetracyclododecanyl group is industrially preferable and an
adamantyl group is more preferable.
In Formula (21), it is more preferable that R.sup.1 represents an
aliphatic cyclic group including at least one or more hydrophilic
groups and preferred examples of the hydrophilic group include a
carbonyl group (preferably a ketonic carbonyl group), an ester
group (--COOR), an alcoholic hydroxyl group, ether (--OR), an imino
group, and an amino group. Among these, from a viewpoint of
availability, a carbonyl group is more preferable.
As the acid dissociable dissolution inhibition group (ii), groups
represented by the following Formulae (4) to (15) can be
exemplified.
##STR00027## ##STR00028##
As the group dissociated by an acid, a repeating unit represented
by the following Formula (16) is preferable as the repeating unit
containing a group in which a hydrogen atom of the alkali-soluble
group (i) is substituted with the acid dissociable dissolution
inhibition group (ii) represented by Formula (21).
##STR00029##
(In the formula, R.sup.2 represents a hydrogen atom, a fluorine
atom, a lower alkyl group having 20 or less carbon atoms, or a
fluorinated lower alkyl group; R.sup.1 represents an aliphatic
cyclic group having 20 or less carbon atoms; and n represents an
integer of 0 or 1 to 5.)
In Formula (16), R.sup.2 represents a hydrogen atom, a fluorine
atom, a lower alkyl group having 20 or less carbon atoms, or a
fluorinated lower alkyl group having 20 or less carbon atoms, and a
lower alkyl group having 1 to 4 carbon atoms or a fluorinated lower
alkyl group having 1 to 4 carbon atoms is preferable. Specific
examples thereof include a methyl group, an ethyl group, a propyl
group, a butyl group, and a trifluoromethyl group. Among these,
from a viewpoint of availability at a low cost, a hydrogen atom or
a methyl group is preferable. n represents an integer of 0 or 1 to
5, and 0 or 1 is preferable.
As a preferred example of the repeating unit represented by Formula
(16), a repeating unit represented by the following Formula (17) is
exemplified.
##STR00030##
(In the formula, R.sup.2 has the same definition as that for
R.sup.2 in Formula (16), and X represents two hydrogen atoms or one
oxygen atom. n' represents 0 or 1. That is, when X represents two
hydrogen atoms, X represents a methylene chain (--CH.sub.2--).)
As a preferred example of the repeating unit represented by Formula
(17), repeating units represented by the following Formulae (18) to
(20) are exemplified. In the formula, R.sup.2 has the same
definition as that for R.sup.2 in Formula (16).
##STR00031##
As another group dissociated by an acid used in the present
invention, a repeating unit which includes a group dissociated by
an acid, from among compounds described in paragraphs "0039" to
"0049" of JP2008-197480A, is preferable, and compounds described in
paragraphs "0052" to "0056" of JP2012-159830A (JP5191567B) are
preferable. In addition, these contents are incorporated in the
specification of the present application.
Hereinafter, specific examples of the repeating unit (a1) which is
included in the specific resin (A) and has a group dissociated by
an acid will be shown, but the present invention is not limited
thereto.
##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036##
##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041##
##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046##
##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051##
##STR00052## ##STR00053## ##STR00054## ##STR00055##
##STR00056##
In the structures shown below, R.sup.21 has the same definition as
that for R.sup.1 in Formula (B.sup.1-1).
##STR00057## ##STR00058## ##STR00059##
As particularly preferred examples of the repeating unit (a1), the
following repeating units are exemplified. Among those, (a1-1) and
(a1-2) are particularly preferable as repeating units represented
by Formula (1). As a repeating unit represented by Formula
(B.sup.1-1), (a1-3) is preferable. As a repeating unit represented
by Formula (B1-2), (a1-4) is preferable.
##STR00060##
In all monomer units constituting the specific resin A, the content
of monomer units forming the repeating unit (a1) is preferably in a
range of 5% by mole to 80% by mole, more preferably in a range of
10% by mole to 70% by mole, and particularly preferably in a range
of 10% by mole to 60% by mole. When the repeating unit (a1) is
contained in the above-described proportion, a photosensitive resin
composition which has high sensitivity and whose exposure latitude
is wide can be obtained. The specific resin A may contain one kind
of repeating unit (a1) or may contain two or more kinds of
repeating unit (a1).
Constituent Unit (a3) Having Crosslinking Group
The specific resin A in the present invention may include a
constituent unit having a crosslinking group (hereinafter, also
appropriately referred to as a "constituent unit (a3)). In regard
to the details of the crosslinking group, the description in
paragraphs "0032" to "0046" of JP2011-209692A can be referred to
and these contents are incorporated in the specification of the
present application.
As the specific resin A used in the present invention, an
embodiment which includes the constituent unit (a3) having a
crosslinking group is also preferable, but a configuration in which
substantially no constituent units (a3) having a crosslinking group
are contained is preferable. When the above-described configuration
is formed, effective removal becomes possible after patterning.
Here, the term "substantially" indicates 3% by mole or less and
preferably 1% by mole with respect to all repeating units of the
specific resin A.
Other Constituent Units (a2)
The specific resin A may contain other constituent units (a2)
(hereinafter, also appropriately referred to as a "constituent unit
(a2)") within a range not disturbing the effects of the present
invention.
As a radical polymerizable monomer used to form the constituent
unit (a2), compounds described in paragraphs "0021" to "0024" of
JP2004-264623 can be exemplified.
Preferred examples of the constituent unit (a2) include a
constituent unit derived from at least one selected from a group
consisting of hydroxyl group-containing unsaturated carboxylic acid
esters, alicyclic structure-containing unsaturated carboxylic acid
esters, styrene, and N-substituted maleimide.
In addition, a constituent unit containing an acid group is
exemplified. Examples of the acid group include a carboxyl group, a
sulfonic acid group, and a phosphoric acid group, and a carboxyl
group is preferable.
Among these, alicyclic structure-containing (meth)acrylic acid
esters such as benzyl (meth)acrylate,
tricyclo[5.2.1.0.sup.2,6]decane-8-yl (meth)acrylate,
tricyclo[5.2.1.0.sup.2,6]decane-8-yloxyethyl (meth)acrylate,
isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, or
2-methylcyclohexyl (meth)acrylate; (meth)acrylic acids; and a
hydrophobic monomer such as styrene are preferable. From a
viewpoint of sensitivity, 2-hydroxyethyl (meth)acrylate and
N-substituted maleimide (meth)acrylates are preferable. Among
these, (meth)acrylic acid esters having an alicyclic structure are
more preferable. Further, from a viewpoint of ethylene resistance,
styrenes such as styrene and .alpha.-methylstyrene are
preferable.
These constituent units (a2) can be used alone or in combination of
two or more kinds thereof. Preferred examples of the combination of
two or more kinds of constituent unit (a2) include a combination of
a constituent unit derived from an alicyclic structure-containing
unsaturated carboxylic acid and a constituent unit derived from
(meth)acrylic acid.
In all monomers constituting the specific resin A, the content of
the monomer units that form the constituent unit (a2) in a case
where the constituent unit (a2) is contained is preferably 1% by
mole to 60% by mole, more preferably in a range of 5% by mole to
50% by mole, and particularly preferably in a range of 5% by mole
to 40% by mole.
The weight average molecular weight of the specific resin A in the
present invention is preferably in a range of 1,000 to 100,000 and
more preferably in a range of 2,000 to 50,000.
Moreover, various methods in regard to a synthesis method of the
specific resin A are known. As an example thereof, the specific
resin A can be synthesized by polymerizing a radical polymerizable
monomer mixture containing radical polymerizable monomers used to
form at least a repeating unit (a1) and a constituent unit (a2) in
an organic solvent using a radical polymerization initiator.
In addition, as the specific resin, a copolymer obtained by adding
2,3-dihydrofuran to an acid anhydride group in a precursor
copolymer formed by copolymerizing unsaturated polyvalent
carboxylic anhydrides in a temperature range of room temperature
(25.degree. C.) to 100.degree. C. in the absence of an acid
catalyst is preferable.
In the present invention, the following resins are shown as
preferred examples of the specific resin A.
BzMA/THFMA/t-BuMA (molar ratio: 20 to 60:35 to 65:5 to 30)
BzMA/THFAA/t-BuMA (molar ratio: 20 to 60:35 to 65:5 to 30)
BzMA/THPMA/t-BuMA (molar ratio: 20 to 60:35 to 65:5 to 30)
BzMA/PEES/t-BuMA (molar ratio: 20 to 60:35 to 65:5 to 30)
BzMA/t-BuMA/MA (molar ratio: 20 to 60:35 to 65:5 to 30)
PMA/t-BuMA/MA (molar ratio: 20 to 60:35 to 65:5 to 30)
The content of the specific resin A in the photosensitive resin
composition of the present invention is preferably in a range of
20% by mass to 99% by mass, more preferably in a range of 40% by
mass to 99% by mass, and still more preferably in a range of 70% by
mass to 99% by mass with respect to total solid contents of the
photosensitive resin composition. When the content thereof is in
the above-described range, pattern formability at the time of
development becomes excellent. Only one specific resin A or two or
more kinds of specific resin may be included.
Moreover, resins other than the specific resin A may be combined
with the photosensitive resin composition of the present invention
within a range not disturbing the effects of the present invention.
In this case, it is preferable that the content of the resins other
than specific resin A is smaller than the content of the specific
resin A from a viewpoint of developability.
Photoacid generator which is decomposed in an amount of 80% by mole
or greater when exposed to light under a condition of 100
mJ/cm.sup.2 or greater at a wavelength of 365 nm
The photosensitive resin composition of the present invention
contains a photoacid generator (specific photoacid generator) which
is decomposed in an amount of 80% by mole or greater when exposed
to light under the condition of 100 mJ/cm.sup.2 or greater at a
wavelength of 365 nm.
The decomposition ratio of the specific photoacid generator can be
acquired by forming a chemically amplified photosensitive resin
composition having a film thickness of 700 nm on a silicon wafer,
heating the wafer at 100.degree. C. for 1 minute, exposing the
wafer to light under the condition of 100 mJ/cm.sup.2 at a
wavelength of 365 nm, and immersing the substrate, heated at
100.degree. C. for 1 minute, in a solution having a ratio of
"methanol/THF=50/50" for 10 minutes while ultrasonic waves are
applied thereto. The decomposition rate of the photoacid generator
can be acquired through calculation using the following formula by
analyzing an extract with HPLC. Decomposition rate (%)=Amount of
decomposition product (mol)/Feed amount (mol).times.100
The specific photoacid generator used in the present invention is
not particularly limited as long as 80% by mole or greater thereof
is decomposed when exposed to light under the condition of 100
mJ/cm.sup.2 or greater at a wavelength of 365 nm, and it is
preferable that 85% by mole or greater thereof is decomposed when
exposed to light under the condition of 100 mJ/cm.sup.2 to 200
mJ/cm.sup.2.
As the specific photoacid generator, a non-ionic photoacid
generator which generates an acid having a pKa of -6 or less using
irradiation with active rays or radiation and whose molar
absorption coefficient at a wavelength of 365 nm is 4000 L/(molcm)
or greater is preferable, a non-ionic photoacid generator which
generates an acid having a pKa of -6 or less using irradiation with
active rays or radiation and whose molar absorption coefficient at
a wavelength of 365 nm is 5000 L/(molcm) or greater is more
preferable, and a non-ionic photoacid generator which generates an
acid having a pKa of -6 or less using irradiation with active rays
or radiation and whose molar absorption coefficient at a wavelength
of 365 nm is 6000 L/(molcm) or greater is still more
preferable.
It is preferable that the specific photoacid generator is a
non-ionic photoacid generator. In addition, the specific photoacid
generator is a compound which includes a fluoroalkyl group chain
having 2 or 3 carbon atoms and is preferably a compound which
includes a fluoroalkyl group having 3 or less carbon atoms and
generates sulfonic acid using irradiation with active rays and/or
radiation. The fluoroalkyl group may be linear, branched, or
cyclic, but it is preferable that the fluoroalkyl group is
linear.
It is preferable that the specific photoacid generator used in the
present invention is a compound including an oxime sulfonate group
(hereinafter, simply referred to as an oxime sulfonate compound).
Further, it is also preferable that the photoacid generator is a
compound including an imide sulfonate group.
<Oxime Sulfonate Compound>
The oxime sulfonate compound is not particularly limited as long as
the compound includes an oxime sulfonate group, and it is
preferable that the oxime sulfonate compound is an oxime sulfonate
compound represented by the following Formula (2), or (OS-103),
(OS-104), (OS-105) or Formula (4) shown below.
##STR00061##
X's in Formula (2) each independently represent an alkyl group, an
alkoxy group, or a halogen atom.
The alkyl group and the alkoxy group as X may include a
substituent. As the alkyl group as X described above, a linear or
branched alkyl group having 1 to 4 carbon atoms is preferable. As
the alkoxy group as X described above, a linear or branched alkoxy
group having 1 to 4 carbon atoms is preferable. As the halogen atom
as X, a chlorine atom or a fluorine atom is preferable.
m in Formula (2) represents an integer of 0 to 3, and 0 or 1 is
preferable. When m represents 2 or 3, a plurality of X's may be the
same as or different from each other.
R.sup.4 in Formula (2) represents an alkyl group or an aryl group.
It is preferable that R.sup.4 represents an alkyl group having 1 to
10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a
halogenated alkyl group having 1 to 5 carbon atoms, a halogenated
alkoxy group having 1 to 5 carbon atoms, a phenyl group which may
be substituted with W, a naphthyl group which may be substituted
with W, or an anthranyl group which may be substituted with W. W
represents a halogen atom, a cyano group, a nitro group, an alkyl
group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10
carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms,
or a halogenated alkoxy group having 1 to 5 carbon atoms.
Specific examples of the alkyl group having 1 to 10 carbon atoms as
R.sup.4 include a methyl group, an ethyl group, an n-propyl group,
an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl
group, a t-butyl group, an n-amyl group, an i-amyl group, an s-amyl
group, an n-hexyl group, an n-heptyl group, an n-octyl group, an
n-nonyl group, and an n-decyl group.
Specific examples of the alkoxy group having 1 to 10 carbon atoms
as R.sup.4 include a methoxy group, an ethoxy group, an n-propoxy
group, an i-propoxy group, an n-butoxy group, an n-amyloxy group,
an n-octyloxy group, and an n-decyloxy group.
Specific examples of the halogenated alkyl group having 1 to 5
carbon atoms as R.sup.4 include a trifluoromethyl group, a
pentafluoroethyl group, a perfluoro-n-propyl group, a
perfluoro-n-butyl group, and a perfluoro-n-amyl group.
Specific examples of the halogenated alkoxy group having 1 to 5
carbon atoms as R.sup.4 include a trifluoromethoxy group, a
pentafluoroethoxy group, a perfluoro-n-propoxy group, a
perfluoro-n-butoxy group, and a perfluoro-n-amyloxy group.
Specific examples of the phenyl group which can be substituted with
W as R.sup.4 include an o-tolyl group, an m-tolyl group, a p-tolyl
group, an o-ethylphenyl group, an m-ethylphenyl group, a
p-ethylphenyl group, a p-(n-propyl)phenyl group, a
p-(i-propyl)phenyl group, a p-(n-butyl)phenyl group, a
p-(i-butyl)phenyl group, a p-(s-butyl)phenyl group, a
p-(t-butyl)phenyl group, a p-(n-amyl)phenyl group, a
p-(i-amyl)phenyl group, a p-(t-amyl)phenyl group, an
o-methoxyphenyl group, an m-methoxyphenyl group, a p-methoxyphenyl
group, an o-ethoxyphenyl group, an m-ethoxyphenyl group, a
p-ethoxyphenyl group, a p-(n-propopxy)phenyl group, a
p-(i-propoxy)phenyl group, a p-(n-butoxy)phenyl group, a
p-(i-butoxy)phenyl group, a p-(s-butoxy)phenyl group, a
p-(t-butoxy)phenyl group, a p-(n-amyloxy)phenyl group, a
p-(i-amyloxy)phenyl group, a p-(t-amyloxy)phenyl group, a
p-chlorophenyl group, a p-bromophenyl group, a p-fluorophenyl
group, a 2,4-dichlorophenyl group, a 2,4-dibromophenyl group, a
2,4-difluorophenyl group, a 2,4,6-dichlorophenyl group, a
2,4,6-tribromophenyl group, a 2,4,6-trifluorophenyl group, a
pentachlorophenyl group, a pentabromophenyl group, a
pentafluorophenyl group, and a p-biphenylyl group.
Specific examples of the naphthyl group which can be substituted
with W as R.sup.4 include a 2-methyl-1-naphthyl group, a
3-methyl-1-naphthyl group, a 4-methyl-1-naphthyl group, a
5-methyl-1-naphthyl group, a 6-methyl-1-naphthyl group, a
7-methyl-1-naphthyl group, an 8-methyl-1-naphthyl group, a
1-methyl-2-naphthyl group, a 3-methyl-2-naphthyl group, a
4-methyl-2-naphthyl group, a 5-methyl-2-naphthyl group, a
6-methyl-2-naphthyl group, a 7-methyl-2-naphthyl group, and an
8-methyl-2-naphthyl group.
Specific examples of the anthranyl group which can be substituted
with W as R.sup.4 include a 2-methyl-1-anthranyl group, a
3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, a
5-methyl-1-anthranyl group, a 6-methyl-1-anthranyl group, a
7-methyl-1-anthranyl group, an 8-methyl-1-anthranyl group, a
9-methyl-1-anthranyl group, a 10-methyl-1-anthranyl group, a
1-methyl-2-anthranyl group, a 3-methyl-2-anthranyl group, a
4-methyl-2-anthranyl group, a 5-methyl-2-anthranyl group, a
6-methyl-2-anthranyl group, a 7-methyl-2-anthranyl group, an
8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a
10-methyl-2-anthranyl group.
In Formula (2), a compound in which m represents 1, X represents a
methyl group, a substitution position of X is an ortho-position,
and R.sup.4 represents a linear alkyl group having 1 to 10 carbon
atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-toluyl
group is particularly preferable.
Specific examples of the oxime sulfonate compound represented by
Formula (2) include a compound (i), a compound (ii), a compound
(iii), and a compound (iv). These compounds may be used alone or in
combination of two or more kinds thereof. The compounds (i) to (iv)
can be obtained as commercially available products. In addition,
specific examples of other oxime sulfonate compounds represented by
Formula (2) will be shown below.
##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066##
##STR00067##
(In Formulae (OS-103) to (OS-105), R.sup.11 represents an alkyl
group, an aryl group, or a heteroaryl group; a plurality of
R.sup.12's each independently represent a hydrogen atom, an alkyl
group, an aryl group, or a halogen atom; a plurality of R.sup.16's
each independently represent a halogen atom, an alkyl group, an
alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or
an alkoxysulfonyl group; X represents O or S; n represents 1 or 2;
and m represents an integer of 0 to 6.)
In Formula (OS-103) to (OS-105), the alkyl group, the aryl group,
or the heteroaryl group represented by R.sup.11 may include a
substituent.
In Formulae (OS-103) to (OS-105), it is preferable that the alkyl
group represented by R.sup.11 is an alkyl group which may include a
substituent and has 1 to 30 carbon atoms.
Examples of the substituent which may be included in the alkyl
group represented by R.sup.11 include a halogen atom, an alkyloxy
group, an aryloxy group, an alkylthio group, an arylthio group, an
alkyloxycarbonyl group, an aryloxycarbonyl group, and an
aminocarbonyl group.
In Formulae (OS-103) to (OS-105), examples of the alkyl group
represented by R.sup.11 include a methyl group, an ethyl group, an
n-propyl group, an i-propyl group, an n-butyl group, an s-butyl
group, a t-butyl group, an n-pentyl group, an n-hexyl group, an
n-octyl group, an n-decyl group, an n-dodecyl group, a
trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl
group, and a benzyl group.
In Formulae (OS-103) to (OS-105), as the aryl group represented by
R.sup.11, an aryl group which may include a substituent and has 6
to 30 carbon atoms is preferable.
Examples of the substituent which may be included in the aryl group
represented by R.sup.11 include a halogen atom, an alkyl group, an
alkyloxy group, an aryloxy group, an alkylthio group, an arylthio
group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an
aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group,
and an alkoxysulfonyl group.
Examples of the aryl group represented by R.sup.11 include a phenyl
group, a p-methylphenyl group, a p-chlorophenyl group, a
pentachlorophenyl group, a pentafluorophenyl group, an
o-methoxyphenyl group, and a p-phenoxyphenyl group.
In Formulae (OS-103) to (OS-105), as the heteroaryl group
represented by R.sup.11, a heteroaryl group which may include a
substituent and has 4 to 30 carbon atoms is preferable.
Examples of the substituent which may be included in the heteroaryl
group represented by R.sup.11 include a halogen atom, an alkyl
group, an alkyloxy group, an aryloxy group, an alkylthio group, an
arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl
group, an aminocarbonyl group, a sulfonic acid group, an
aminosulfonyl group, and an alkoxysulfonyl group.
In Formulae (OS-103) to (OS-105), the heteroaryl group represented
by R.sup.11 may include at least one heteroaromatic ring and, for
example, a heteroaromatic ring and a benzene ring may be
condensed.
The heteroaryl group represented by R.sup.11 may include a
substituent. A group obtained by removing one hydrogen atom from a
ring selected from a group consisting of a thiophene ring, a
pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a
benzothiophene ring, a benzothiazole ring, and a benzimidazole ring
is exemplified.
In Formulae (OS-103) to (OS-105), it is preferable that R.sup.12
represents a hydrogen atom, an alkyl group, or an aryl group and
more preferable that R.sup.12 represents a hydrogen atom or an
alkyl group.
In Formulae (OS-103) to (OS-105), among two or more R.sup.12's
existing in a compound, it is preferable that one or two R.sup.12's
represent an aryl group or a halogen atom, more preferable that one
R.sup.12 represents an alkyl group, an aryl group, or a halogen
atom, and particularly preferable that one R.sup.12 represents an
alkyl group and the rest represent a hydrogen atom.
In Formulae (OS-103) to (OS-105), the alkyl group or the aryl group
represented by R.sup.12 may include a substituent.
Examples of the substituent which may be included in the alkyl
group or the aryl group represented by R.sup.12 are the same as
those of the substituent which may be included in the alkyl group
or the aryl group represented by R.sup.1.
In Formulae (OS-103) to (OS-105), as the alkyl group represented by
R.sup.12, an alkyl group which may include a substituent and has 1
to 12 carbon atoms is preferable and an alkyl group which may
include a substituent and has 1 to 6 carbon atoms is more
preferable.
As the alkyl group represented by R.sup.12, a methyl group, an
ethyl group, an n-propyl group, an i-propyl group, an n-butyl
group, an i-butyl group, an s-butyl group, an n-hexyl group, an
allyl group, a chloromethyl group, a bromomethyl group, a
methoxymethyl group, or a benzyl group is preferable; a methyl
group, an ethyl group, an n-propyl group, an i-propyl group, an
n-butyl group, an i-butyl group, an s-butyl group, or an n-hexyl
group is more preferable; a methyl group, an ethyl group, an
n-propyl group, an n-butyl group, or an n-hexyl group is still more
preferable; and a methyl group is particularly preferable.
In Formulae (OS-103) to (OS-105), as the aryl group represented by
R.sup.12, an aryl group which may include a substituent and has 6
to 30 carbon atoms is preferable.
Preferred examples of the aryl group represented by R.sup.12
include a phenyl group, a p-methylphenyl group, an o-chlorophenyl
group, a p-chlorophenyl group, an o-methoxyphenyl group, and a
p-phenoxyphenyl group.
Examples of the halogen atom represented by R.sup.12 include a
fluorine atom, a chlorine atom, a bromine atom, and iodine atom.
Among these, a chlorine atom or a bromine atom is preferable.
In Formulae (OS-103) to (OS-105), X represents O or S, and it is
preferable that X represents O. In Formulae (OS-103) to (OS-105), a
ring containing X as a ring member is a 5- or 6-membered ring.
In Formulae (OS-103) to (OS-105), n represents 1 or 2. It is
preferable that n represents 1 when X represents 0 and it is
preferable that n represents 2 when X represents S.
In Formulae (OS-103) to (OS-105), the alkyl group and the alkyloxy
group represented by R.sup.16 may include a substituent.
In Formulae (OS-103) to (OS-105), as the alkyl group represented by
R.sup.16, an alkyl group which may include a substituent and has 1
to 30 carbon atoms is preferable.
Examples of the substituent which may be included in the alkyl
group represented by R.sup.16 include a halogen atom, an alkyloxy
group, an aryloxy group, an alkylthio group, an arylthio group, an
alkyloxycarbonyl group, an aryloxycarbonyl group, and an
aminocarbonyl group.
In Formulae (OS-103) to (OS-105), preferred examples of the alkyl
group represented by R.sup.16 include a methyl group, an ethyl
group, an n-propyl group, an i-propyl group, an n-butyl group, an
s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl
group, an n-octyl group, an n-decyl group, an n-dedecyl group, a
trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl
group, and a benzyl group.
In Formulae (OS-103) to (OS-105), as the alkyloxy group represented
by R.sup.16, an alkyloxy group which may include a substituent and
has 1 to 30 carbon atoms is preferable.
Examples of the substituent which may be included in the alkyloxy
group represented by R.sup.16 include a halogen atom, an alkyloxy
group, an aryloxy group, an alkylthio group, an arylthio group, an
alkyloxycarbonyl group, an aryloxycarbonyl group, and an
aminocarbonyl group.
In Formulae (OS-103) to (OS-105), as the alkyloxy group represented
by R.sup.16, a methyloxy group, an ethyloxy group, a butyloxy
group, a hexyloxy group, a phenoxyethyloxy group, a
trichloromethyloxy group, or an ethoxyethyloxy group is
preferable.
Examples of the aminosulfonyl group as R.sup.16 include a
methylaminosulfonyl group, a dimethylaminosulfonyl group, a
phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and
an aminosulfonyl group.
Examples of the alkoxysulfonyl group represented by R.sup.16
include a methoxysulfonyl group, an ethoxysulfonyl group, a
propyloxysulfonyl group, and a butyloxysulfonyl group.
Moreover, in Formulae (OS-103) to (OS-105), m represents an integer
of 0 to 6, preferably represents an integer of 0 to 2, more
preferably represents 0 or 1, and particularly preferably
represents 0.
In addition, it is particularly preferable that the compound
represented by Formula (OS-103) is a compound represented by the
following Formula (OS-106), (OS-110), or (OS-111), the compound
represented by Formula (OS-104) is a compound represented by the
following Formula (OS-107), and the compound represented by Formula
(OS-105) is a compound represented by the following Formula
(OS-108) or (OS-109).
##STR00068##
(In Formulae (OS-106) to (OS-111), R.sup.11 represents an alkyl
group, an aryl group, or a heteroaryl group; R.sup.17 represents a
hydrogen atom or a bromine atom; R.sup.18 represents a hydrogen
atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a
chloromethyl group, a bromomethyl group, a bromoethyl group, a
methoxymethyl group, a phenyl group, or a chlorophenyl group;
R.sup.19 represents a hydrogen atom, a halogen atom, a methyl
group, or a methoxy group, and R.sup.20 represents a hydrogen atom
or a methyl group.)
R.sup.11 in Formulae (OS-106) to (OS-111) has the same definition
as that for R.sup.11 in Formulae (OS-103) to (OS-105) and preferred
embodiments are the same as each other.
R.sup.17 in Formula (OS-106) represents a hydrogen atom or a
bromine atom and preferably represents a hydrogen atom.
R.sup.18 in Formulae (OS-106) to (OS-111) represents a hydrogen
atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a
chloromethyl group, a bromomethyl group, a bromoethyl group, a
methoxymethyl group, a phenyl group, or a chlorophenyl group,
preferably represents an alkyl group having 1 to 8 carbon atoms, a
halogen atom, or a phenyl group, more preferably represents an
alkyl group having 1 to 8 carbon atoms, still more preferably
represents an alkyl group having 1 to 6 carbon atoms, and
particularly preferably represents a methyl group.
R.sup.19 in Formulae (OS-108) and (OS-109) represents a hydrogen
atom, a halogen atom, a methyl group, or a methoxy group and
preferably represents a hydrogen atom.
R.sup.20 in Formulae (OS-108) to (OS-111) represents a hydrogen
atom or a methyl group and preferably represents a hydrogen
atom.
Moreover, the above-described oxime sulfonate compound may have one
or a mixture of oxime steric structures (E, Z).
Specific examples of the oxime sulfonate compounds represented by
Formula (OS-103) to (OS-105) include the following exemplary
compounds shown below, but the present invention is not limited
thereto.
##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073##
##STR00074## ##STR00075## ##STR00076## ##STR00077##
As another preferred embodiment of an oxime sulfonate compound
which includes at least one oxime sulfonate group, a compound
represented by the following Formula (OS-101) is exemplified.
##STR00078##
In Formula (OS-101), R.sup.11 represents a hydrogen atom, an alkyl
group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group,
an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group,
a cyano group, an aryl group, or a heteroaryl group. R.sup.12
represents an alkyl group or an aryl group.
X represents --O--, --S--, --NH--, --NR.sup.15--, --CH.sub.2--,
--CR.sup.16H--, or --CR.sup.16R.sup.17--, and R.sup.15 to R.sup.17
each independently represent an alkyl group or an aryl group.
R.sup.21 to R.sup.24 each independently represent a hydrogen atom,
a halogen atom, an alkyl group, an alkenyl group, an alkoxy group,
an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an
arylcarbonyl group, an amide group, a sulfo group, a cyano group,
or an aryl group. Two of R.sup.21 to R.sup.24 may be bonded to each
other to form a ring.
As R.sup.21 to R.sup.24, a hydrogen atom, a halogen atom, or an
alkyl group is preferable and an embodiment in which at least two
of R.sup.21 to R.sup.24 are bonded to each other to form an aryl
group is preferably exemplified. Among these, from a viewpoint of
sensitivity, an embodiment in which all of R.sup.21 to R.sup.24
represent a hydrogen atom is preferable.
Any of the above-described substituents may further include a
substituent.
It is more preferable that the compound represented by Formula
(OS-101) above is a compound represented by the following Formula
(OS-102).
##STR00079##
In Formula (OS-102), R.sup.11, R.sup.12, and R.sup.21 to R.sup.24
respectively have the same definitions as those for R.sup.11,
R.sup.12, and R.sup.21 to R.sup.24 in Formula (SO-101), and
preferred examples are the same as each other.
Among these, an embodiment in which R.sup.11 in Formulae (OS-101)
and (OS-102) represents a cyano group or an aryl group is more
preferable and an embodiment which is represented by Formula
(OS-102) and R.sup.11 represents a cyano group, a phenyl group, or
a naphthyl group is most preferable.
Moreover, the above-described oxime sulfonate compound may have one
or a mixture of steric structures (E, Z, and the like) of oxime or
a benzothiazole ring.
Hereinafter, specific examples (exemplary compounds b-1 to b-34) of
the compounds represented by Formula (OS-101) which can be suitably
used in the present invention will be shown, but the present
invention is not limited thereto. Further, in the specific
examples, Me represents a methyl group, Et represents an ethyl
group, Bn represents a benzyl group, and Ph represents a phenyl
group.
##STR00080## ##STR00081## ##STR00082## ##STR00083##
##STR00084##
Among the above-described compounds, from a viewpoint of
compatibility of sensitivity and stability, compounds b-9, b-16,
b-31, and b-33 are preferable.
Examples of commercially available products thereof include
WPAG-336 (manufactured by Wako Pure Chemical Industries, Ltd.),
WPAG-443 (the following structure, manufactured by Wako Pure
Chemical Industries, Ltd.), and MBZ-101 (the following structure,
manufactured by Midori Kagaku Co., Ltd.).
<<Compound Represented by Formula (4)>>
##STR00085##
In Formula (4), R.sup.8 represents a fluoroalkyl group having 2 or
3 carbon atoms, R.sup.9 represents an alkyl group having 1 to 8
carbon atoms or a fluoroalkyl group, and R.sup.10 represents an
aromatic hydrocarbon group or an aromatic heterocyclic group.
In Formula (4), it is preferable that R.sup.8 represents a
perfluoroalkyl group having 2 or 3 carbon atoms.
It is preferable that R.sup.9 represents an alkyl group having 3 to
8 carbon atoms or a fluoroalkyl group and a perfluoroalkyl group
having 3 to 8 carbon atoms is preferable.
It is preferable that R.sup.10 represents an aromatic hydrocarbon
group. The aromatic hydrocarbon group may be a single ring or a
condensed ring, and a condensed ring is preferable. The number of
carbon atoms of the aromatic hydrocarbon group is preferably in a
range of 6 to 30, more preferably in a range of 6 to 18, and still
more preferably in a range of 6 to 15. It is preferable that the
aromatic hydrocarbon group is a fluorene ring.
When R.sup.10 represents an aromatic heterocyclic group, the
aromatic heterocyclic group may be a single ring or a condensed
ring. The number of carbon atoms of the aromatic heterocyclic group
is preferably in a range of 6 to 30, more preferably in a range of
6 to 18, and still more preferably in a range of 6 to 15.
It is preferable that the compound represented by Formula (4) is
represented by Formula (4-1).
##STR00086##
In Formula (4-1), R.sup.8 represents a fluoroalkyl group having 2
or 3 carbon atoms, R.sup.9 represents an alkyl group having 1 to 8
carbon atoms, or a fluoroalkyl group, and R.sup.11 to R.sup.19 each
independently represent a hydrogen atom or an alkyl group.
R.sup.8 and R.sup.9 have the same definitions as those for R.sup.8
and R.sup.9 in Formula (4) and preferred ranges are the same as
each other.
It is preferable that R.sup.11 to R.sup.19 represent a hydrogen
atom.
When R.sup.11 to R.sup.19 represent an alkyl group, the number of
carbon atoms of the alkyl group is preferably in a range of 1 to
30.
As specific examples of the compound represented by Formula (4),
the following exemplary compounds are exemplified, but the present
invention is not limited thereto.
##STR00087##
<Compound Having Imide Sulfonate Group>
It is preferable that a compound including an imide sulfonate group
which can be used as a specific photoacid generator is a compound
including a 5-membered ring imide sulfonate group. Moreover, it is
preferable that a compound including an imide sulfonate group is a
compound represented by the following Formula (3).
##STR00088##
In Formula (3), R.sup.6 represents a fluoroalkyl group having 2 or
3 carbon atoms and R.sup.7 represents an alkylene group, an
alkenylene group, or an arylene group.
In Formula (3), it is preferable that R.sup.6 represents a
perfluoroalkyl group having 2 or 3 carbon atoms.
In Formula (3), R.sup.7 represents an alkylene group, an alkenylene
group, or an arylene group.
The alkylene group may be linear, branched, or cyclic and a cyclic
alkylene group is preferable.
The alkenyl group may be linear, branched, or cyclic and cyclic is
preferable. The number of carbon atoms of the alkylene group is
preferably in a range of 1 to 12, more preferably in a range of 3
to 12, and still more preferably in a range of 3 to 8. The number
of carbon atoms of the alkenylene group is preferably in a range of
2 to 12, more preferably in a range of 3 to 12, and still more
preferably in a range of 3 to 8.
The number of carbon atoms of the arylene group is preferably in a
range of 6 to 18 and more preferably in a range of 6 to 12.
It is preferable that a compound including an imide sulfonate group
is a compound including a 5-membered ring imide sulfonate group and
a norbornene group.
As a commercially available product of the compound including an
imide sulfonate group, NT-1TF or NT3TF (manufactured by San-Apro
Ltd.) can be used.
In addition, as specific examples of other compounds including an
imide sulfonate group, the following exemplary compounds are
exemplified, but the present invention is not limited thereto.
##STR00089##
It is preferable that the photosensitive resin composition of the
present invention does not contain a 1,2-quinonediazide compound as
a photo acid generator that responds to active rays. The reason for
this is that a 1,2-quinonediazide compound generates a carboxy
group using a sequential photochemical reaction, but the quantum
yield is 1 or less and thus the sensitivity is low compared to an
oxime sulfonate compound.
On the contrary, it is assumed that the oxime sulfonate compound
acts as a catalyst with respect to deprotection of an acid group
which is protected in which an acid is generated by the compound
responding to active rays, and thus an acid generated due to an
action of one light quantum contributes to deprotection reaction
multiple times, the quantum yield exceeds 1 and becomes a large
value, for example, a multiple of 10, and then high sensitivity is
obtained as a result of so-called chemical amplification.
Further, since the oxime sulfonate compound has a .pi. conjugated
system which is extended, the compound has absorption on a long
wavelength side and extremely high sensitivity is shown with
respect to not only deep ultraviolet (DUV) and i-line but also
g-line.
In the photosensitive resin composition of the present invention,
an amount of acid decomposition greater than or equal to that for
acetal or ketal can be obtained using a tetrahydrofuranyl group as
an acid decomposable group in the specific resin. In this manner,
the acid decomposable group can be reliably consumed through
post-baking over a shorter period of time. In addition, since the
sulfonic acid generation rate is increased when an oxime sulfonate
compound which is a photoacid generator is combined and then used,
generation of an acid is promoted and decomposition of an acid
decomposable group of a resin is promoted. Further, in acids
obtained through decomposition of the oxime sulfonate compound,
since a sulfonic acid with small molecules is generated,
diffusibility in a curing film becomes improved and thus
sensitivity can be increased.
The specific photoacid generator may be used alone or in
combination of two or more kinds thereof. In addition, the specific
photoacid generator can be used by being combined with another kind
of specific photo acid generator.
In the photosensitive resin composition in the present invention,
the content of the specific photoacid generator used is preferably
in a range of 0.1% by mass to 20% by mass and more preferably in a
range of 0.5% by mass to 18% by mass with respect to total solid
content of the photoacid resin composition.
The content of the specific photoacid generator can be suitably
selected according to the film thickness of the water-soluble resin
film. In a case where the film thickness of the water-soluble resin
film is less than 2 .mu.m, since the specific photoacid generator
is unlikely to diffuse into the water-soluble resin film, a desired
mask shape can be easily obtained even when the content of the
specific photoacid generator is set to be in a range of 0.5% by
mass to 2% by mass. Meanwhile, in a case where the film thickness
of the water-soluble resin film is 2 .mu.m or greater, since the
specific photoacid generator easily diffuses into the water-soluble
resin film, it is preferable that the content of the specific
photoacid generator is set to be in a range of 2% by mass to 18% by
mass in order to obtain a desired mask shape. Further, a more
excellent mask shape can be obtained by setting the addition amount
of the specific photoacid generator to be 18% by mass or less.
Other Components
The photosensitive resin composition of the present invention may
contain other components.
As other components, it is preferable that a solvent is contained
in the photosensitive resin composition from a viewpoint of coating
properties.
Solvent
It is preferable that the photosensitive resin composition of the
present invention contains a solvent.
In the photosensitive resin composition of the present invention,
it is preferable that a solution obtained by dissolving a specific
resin and a specific photoacid generator which are essential
components, and optional compositions of various additives in a
solvent is prepared.
A known solvent can be used as the solvent to be used for the
photosensitive resin composition of the present invention, and
examples thereof include ethylene glycol monoalkyl ethers, ethylene
glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates,
propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers,
propylene glycol monoalkyl ether acetates, diethylene glycol
dialkyl ethers, diethylene glycol monoalkyl ether acetates,
dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl
ethers, dipropylene glycol monoalkyl ether acetates, esters,
ketones, amides, and lactones.
Examples of the solvent to be used for the photosensitive resin
composition of the present invention include (1) ethylene glycol
monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene
glycol monoethyl ether, ethylene glycol monopropyl ether, and
ethylene glycol monobutyl ether; (2) ethylene glycol dialkyl ethers
such as ethylene glycol dimethyl ether, ethylene glycol diethyl
ether, and ethylene glycol dipropyl ether; (3) ethylene glycol
monoalkyl ether acetates such as ethylene glycol monomethyl ether
acetate, ethylene glycol monoethyl ether acetate, ethylene glycol
monopropyl ether acetate, and ethylene glycol monobutyl ether
acetate; (4) propylene glycol monoalkyl ethers such as propylene
glycol monomethyl ether, propylene glycol monoethyl ether,
propylene glycol monopropyl ether, and propylene glycol monobutyl
ether; (5) propylene glycol dialkyl ethers such as propylene glycol
dimethyl ether, propylene glycol diethyl ether, diethylene glycol
monomethyl ether, and diethylene glycol monoethyl ether;
(6) propylene glycol monoalkyl ether acetates such as propylene
glycol monomethyl ether acetate, propylene glycol monoethyl ether
acetate, propylene glycol monopropyl ether acetate, and propylene
glycol monobutyl ether acetate, (7) diethylene glycol dialkyl
ethers such as diethylene glycol dimethyl ether, diethylene glycol
diethyl ether, and diethylene glycol ethyl methyl ether; (8)
diethylene glycol monoalkyl ether acetates such as diethylene
glycol monomethyl ether acetate, diethylene glycol monoethyl ether
acetate, diethylene glycol monopropyl ether acetate, and diethylene
glycol monobutyl ether acetate; (9) dipropylene glycol monoalkyl
ethers such as dipropylene glycol monomethyl ether, dipropylene
glycol monoethyl ether, dipropylene glycol monopropyl ether, and
dipropylene glycol monobutyl ether; (10) dipropylene glycol dialkyl
ethers such as dipropylene glycol dimethyl ether, dipropylene
glycol diethyl ether, and dipropylene glycol ethyl methyl
ether;
(11) dipropylene glycol monoalkyl ether acetates such as
dipropylene glycol monomethyl ether acetate, dipropylene glycol
monoethyl ether acetate, dipropylene glycol monopropyl ether
acetate, and dipropylene glycol monobutyl ether acetate; (12)
lactates such as methyl lactate, ethyl lactate, n-propyl lactate,
isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl
lactate, and isoamyl lactate; (13) aliphatic carboxylates such as
n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate,
n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl
propionate, isopropyl propionate, n-butyl propionate, isobutyl
propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate,
isopropyl butyrate, n-butyl butyrate, and isobutyl butyrate; (14)
esters such as ethyl hydroxyacetate, ethyl
2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate,
ethyl methoxyacetate, ethyl ethoxyacetate, methyl
3-methoxypropionate, ethyl 3-methoxypropionate, methyl
3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxy butyl
acetate, 3-methyl-3-methoxy butyl acetate, 3-methyl-3-methoxy butyl
propionate, 3-methyl-3-methoxy butyl butyrate, methyl acetoacetate,
ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate;
(15) ketones such as methyl ethyl ketone, methyl propyl ketone,
methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone,
3-heptanone, 4-heptanone, and cyclohexanone; (16) amides such as
N-methylformamide, N,N-dimethylformamide, N-methylacetamide,
N,N-dimethylacetamide, and N-methylpyrrolidone; and (17) lactones
such as .gamma.-butyrolactone.
Moreover, in addition to these solvents, solvents such as benzyl
ethyl ether, dihexyl ether, ethylene glycol monophenyl ether
acetate, diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether, isophorone, caproic acid, caprylic acid,
1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate,
ethyl benzoate, diethyl oxalate, diethyl maleate, or ethylene
carbonate, and propylene carbonate can be added as needed.
Among the above-described solvents, propylene glycol monoalkyl
ether acetates and/or diethylene glycol dialkyl ethers are
preferable, and diethylene glycol ethyl methyl ether and/or
propylene glycol monomethyl ether acetate are particularly
preferable.
These solvents can be used alone or in combination of two or more
kinds thereof.
In a case where the photosensitive resin composition of the present
invention contains a solvent, the content of the solvent is
preferably in a range of 1 part by weight to 3000 parts by weight,
more preferably in a range of 5 parts by weight to 2000 parts by
weight, and still more preferably in a range of 10 parts by weight
to 1500 parts by weight with respect to 100 parts by weight of the
specific resin.
Further, it is preferable that the photosensitive resin composition
of the present invention contains a basic compound from a viewpoint
of liquid storage stability and contains a surfactant from a
viewpoint of coating properties.
Basic Compound
It is preferable that the photosensitive resin composition of the
present invention contains a basic compound.
A basic compound can be arbitrarily selected from compounds used
for chemically amplified resists and then used. Examples thereof
include aliphatic amines, aromatic amines, heterocyclic amines,
quaternary ammonium hydroxide, and quaternary ammonium salts of
carboxylic acids.
As the basic compound, a primary or secondary amine compound is
preferable. Particularly, in a case where the specific resin A
includes a repeating unit represented by Formula (B.sup.1-1) or a
repeating unit represented by Formula (B.sup.1-2), it is preferable
that the basic compound is a primary amine compound.
Examples of the aliphatic amine include trimethylamine,
diethylamine, trimethylamine, di-n-propylamine, tri-n-propylamine,
di-n-pentylamine, tri-n-pentylamine, diethanolamine,
triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and
hexylamine.
Examples of the aromatic amine include aniline, benzylamine,
N,N-dimethylaniline, diphenylamine, 2,6-diisopropylaniline, and
2,4,6-tri-tert-butylaniline.
Examples of the heterocyclic amine include pyridine,
2-methylpyridine, 4-methylpyridine, 2-ethylpyridine,
4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine,
N-methyl-4-phenylpyridine, 4-dimethylaminopyridine,
N,N-dimethyl-4-aminopyridine, imidazole, benzimidazole,
4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole,
nicotine, nicotinic acid, nicotinic acid amide, quinoline,
8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine,
pyrrolidine, piperidine, cyclohexyl morpholinoethyl thiourea,
piperizine, morpholine, 4-methylmorpholine,
1,5-diazabicyclo[4.3.0]-5-nonene, and
1,8-diazabicyclo[5,3,0]-7-undecene.
Examples of the quaternary ammonium hydroxide include
tetramethylammonium hydroxide, tetraethylammonium hydroxide,
tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium
hydroxide.
Examples of the quaternary ammonium salts of carboxylic acid
include tetramethylammonium acetate, tetramethylammonium benzoate,
tetra-n-butylammonium acetate, and tetra-n-butylammonium
benzoate.
The basic compound which can be used in the present invention may
be used alone or in combination of two or more kinds thereof, but a
combination of two or more kinds thereof is preferable, a
combination of two kinds thereof is more preferable, and a
combination of two kinds of heterocyclic amine is still more
preferable.
In a case where the photosensitive resin composition of the present
invention contains a basic compound, the content of the basic
compound is preferably in a range of 0.001 parts by weight to 1
part by weight and more preferably in a range of 0.002 parts by
weight to 0.2 parts by weight with respect to 100 parts by weight
of the specific resin.
Surfactant
It is preferable that the photosensitive resin composition of the
present invention contains a surfactant.
As the surfactant, any of an anionic surfactant, a cationic
surfactant, a non-ionic surfactant, and an amphoteric surfactant
can be used, but a preferable surfactant is a non-ionic
surfactant.
Examples of the non-ionic surfactant include polyoxyethylene higher
alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher
fatty acid diesters of polyoxyethylene glycol, a fluorine-based
surfactant, and a silicone-based surfactant.
It is more preferable that the photosensitive resin composition of
the present invention contains a fluorine-based surfactant and/or a
silicone-based surfactant as a surfactant.
As the fluorine-based surfactant and the silicone-based surfactant,
surfactants described in JP1987-36663A (JP-S62-36663A),
JP1986-226746A (JP-S61-226746A), JP1986-226745A (JP-S61-226745A),
JP1987-170950A (JP-S62-170950A), JP1988-34540A (JP-S63-34540A),
JP1995-230165A (JP-H7-230165A), JP1996-62834A (JP-H8-62834A),
JP1997-54432A (JP-H9-54432A), JP1997-5988A (JP-H9-5988A), and
JP2001-330953A can be exemplified, and commercially available
products can be also used.
Examples of the commercially available products which can be used
include fluorine-based surfactants and silicone based surfactants
such as F TOP EF301 and F TOP EF303 (both manufactured by Shin
Akita Kasei Inc.), Fluorad FC430 and Fluorad FC431 (both
manufactured by Sumitomo 3M Limited), Megaface F171, Megaface F173,
Megaface F176, Megaface F189, and Megaface R08 (all manufactured by
DIC Corporation), Surflon S-382, Surflon SC101, Surflon SC102,
Surflon SC103, Surflon SC104, Surflon SC105, and Surflon SC106 (all
manufactured by ASAHI GLASS CO., LTD.), and the PF-6320 PolyFox
Series of and the like (manufactured by OMNOVA Solution Inc.). In
addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu
Chemical Co., Ltd.) can be also used as a silicone-based
surfactant. Moreover, acetylene E00 (manufactured by Kawaken Fine
Chemicals Co., Ltd.) can be also used.
Further, as a surfactant, a copolymer which contains a constituent
unit A and a constituent unit B which are represented by the
following Formula (1) and whose weight average molecular weight
(Mw) measured by gel permeation chromatography in terms of
polystyrene is in a range of 1000 to 10000 in a case where
tetrahydrofuran (THF) is used as a solvent is exemplified.
##STR00090##
(In Formula (1), R.sup.1 and R.sup.3 each independently represent a
hydrogen atom or a methyl group; R.sup.2 represents a linear
alkylene group having 1 to 4 carbon atoms; R.sup.4 represents a
hydrogen atom or an alkyl group having 1 to 4 carbon atoms; L
represents an alkylene group having 3 to 6 carbon atoms, p and q
represent the weight percentages showing a weight ratio; p
represents a numerical value of 10% by mass to 80% by mass; q
represents a numerical value of 20% by mass to 90% by mass; r
represents an integer of 1 to 18; and n represents an integer of 1
to 10.)
It is preferable that L represents a branched alkylene group
represented by the following Formula (2). R.sup.5 in Formula (2)
represents an alkyl group having 1 to 4 carbon atoms, and an alkyl
group having 1 to 3 carbon atoms is preferable and an alkyl group
having 2 or 3 carbon atoms is more preferable in terms of
compatibility and wettability with respect to a surface to be
coated.
##STR00091##
The weight average molecular weight (Mw) of the copolymer is more
preferably in a range of 1500 to 5000.
These surfactants can be used alone or in combination of two or
more kinds thereof.
In a case where the photosensitive resin composition of the present
invention contains a surfactant, the amount of the surfactant to be
added is preferably 10 parts by weight or less, more preferably in
a range of 0.01 parts by weight to 10 parts by weight, and still
more preferably in a range of 0.01 parts by weight to 1 part by
weight with respect to 100 parts by weight of the specific
resin.
Moreover, if necessary, known additives such as an antioxidant, a
plasticizer, a thermal radical generator, a thermal acid generator,
an acid proliferation agent, an ultraviolet absorber, a thickener,
and an organic or inorganic precipitation inhibitor can be added to
the photosensitive resin composition of the present invention. The
description of paragraphs "0143" to "0148" of JP2011-209692A can be
referred to for details and the contents are incorporated in the
specification of the present application.
The film thickness of the resist film is preferably in a range of
100 nm to 1000 nm and more preferably in a range of 300 nm to 850
nm from a viewpoint of improving resolving power. Such a film
thickness can be obtained by setting the solid content
concentration in a chemically amplified photosensitive resin
composition to be in an appropriate range, allowing the composition
to have a suitable viscosity, and improving coating properties and
film forming properties.
<Method of Patterning Organic Semiconductor Film>
A method of patterning an organic semiconductor film of the present
invention includes:
(1) a process of forming a water-soluble resin film on the organic
semiconductor film;
(2) a process of forming a resist film, on the water-soluble resin
film that is on the opposite side of the organic semiconductor
film, which contains a photoacid generator that is decomposed in an
amount of 80% by mole or greater when exposed to light under the
condition of 100 mJ/cm.sup.2 or greater at a wavelength of 365 nm
and is formed of a chemically amplified photosensitive resin
composition;
(3) a process of exposing the resist film;
(4) a process of performing development using a developer
containing an organic solvent to prepare a mask pattern;
(5) a process of removing at least the water-soluble resin film and
the organic semiconductor film of a non-mask portion during an
etching treatment; and
(6) a process of dissolving the water-soluble resin film using
water.
<<(1) Process of Forming Water-Soluble Resin Film on Organic
Semiconductor Film>>
The method of patterning the organic semiconductor film of the
present invention includes a process of forming a water-soluble
resin film 3 on an organic semiconductor film 2 as illustrated in
FIG. 1(B). The present process is normally performed after the
organic semiconductor film 2 is formed on the substrate 1 as
illustrated in FIG. 1(A). In this case, the water-soluble resin
film is formed on a surface that is the opposite side to the
surface on the substrate side of the organic semiconductor. The
water-soluble resin film is normally provided on the surface of the
organic semiconductor film, but another layer may be provided
within the range not departing from the scope of the present
invention. Specifically, a water-soluble undercoat layer is
exemplified. In addition, only one sheet or two or more sheets of
water-soluble resin films may be provided.
<<(2) Process of Forming Resist Film, on Water-Soluble Resin
Film on Opposite Side of Organic Semiconductor Film, which Contains
Photoacid Generator that is Decomposed in an Amount of 80% by Mole
or Greater when Exposed to Light Under a Condition of 100
mJ/Cm.sup.2 or Greater at Wavelength of 365 nm and is Formed of a
Chemically Amplified Photosensitive Resin Composition>>
After the process (1), in a process (2) a resist film formed of a
chemically amplified photosensitive resin composition is formed on
the water-soluble resin film on the opposite side to the surface of
the organic semiconductor side. The resist film is normally formed
by applying the chemically amplified photosensitive resin
composition to the surface of the water-soluble resin film, but may
be formed via a film such as an undercoat layer. The description of
the water-soluble resin composition can be referred to for a method
of applying the chemically amplified photosensitive resin
composition.
The chemically amplified photosensitive resin composition used in
the present invention contains a photoacid generator which is
decomposed in an amount of 80% by mole or greater when exposed to
light under the condition of 100 mJ/cm.sup.2 or greater at a
wavelength of 365 nm. When such a photo acid generator is mixed, an
acid is generated when the acid generator is exposed to light, a
specific resin described below contained in the resist reacts with
the acid, patterning becomes possible, and a resist film
functions.
The solid content concentration of the chemically amplified
photosensitive resin composition is normally in a range of 1.0% by
mass to 20% by mass, preferably in a range of 1.5% by mass to 17%
by mass, and more preferably in a range of 2.0% by mass to 15% by
mass. When the solid content concentration is set to be in the
above-described range, the water-soluble resin film can be
uniformly coated with a resist solution and a resist pattern which
has high resolution and a rectangular profile can be formed. The
solid content concentration is a weight percentage showing the
weight of other resist components other than the solvent with
respect to the total weight of the resin composition.
<<(3) Process of Exposing Resist Film>>
After the resist film is formed by the process (2), the resist film
is exposed. Specifically, the resist film is irradiated with active
rays through a mask having a predetermined pattern. The resist film
may be exposed only once or multiple times.
Specifically, a substrate provided with a dried coating film of the
photosensitive resin composition is irradiated with active rays
having a predetermined pattern. The substrate may be exposed to
light through a mask or the predetermined pattern may be directly
drawn. Active rays having a wavelength of 300 nm to 450 nm and
preferably a wavelength of 365 nm are preferably used. After this
process, a heating process after exposure (PEB) may be performed as
needed.
A low-pressure mercury lamp, a high-pressure mercury lamp, an
ultra-high pressure mercury lamp, a chemical lamp, a laser
generator, or an LED light source can be used for exposure using
active rays.
In a case where a mercury lamp is used, active rays having a
wavelength of g-line (436 nm), a wavelength of i-line (365 nm), and
a wavelength of h-line (405 nm) are preferably used. A mercury lamp
is preferable compared to a laser in terms of suitability for
exposure of a large area.
In a case of using a laser, a solid (YAG) laser having a wavelength
of 343 nm or 355 nm is preferably used, an excimer laser having a
wavelength of 351 nm (XeF) is preferably used, and a semiconductor
laser having a wavelength of 375 nm or 405 nm is preferably used.
Among these, a wavelength of 355 nm or 405 nm is more preferable in
terms of stability or costs. A coating film can be irradiated with
a laser once or multiple times.
The energy density per pulse of a laser is preferably in a range of
0.1 mJ/cm.sup.2 to 10000 mJ/cm.sup.2. In order for the coating film
to be sufficiently cured, the energy density thereof is more
preferably 0.3 mJ/cm.sup.2 or greater and most preferably 0.5
mJ/cm.sup.2 or greater. In order for the coating film not to be
decomposed by an ablation phenomenon, the energy density is more
preferably 1000 mJ/cm.sup.2 or less and most preferably 100
mJ/cm.sup.2 or less.
Further, the pulse width is preferably in a range of 0.1 nsec to
30000 nsec. In order for the coloring film not to be decomposed by
an ablation phenomenon, the pulse width is more preferably 0.5 nsec
or greater and most preferably 1 nsec or greater. Further, in order
to improve aligning accuracy at the time of scanning exposure, the
pulse width is more preferably 1000 nsec or less and most
preferably 50 nsec or less.
In addition, the frequency of the laser is preferably in a range of
1 Hz to 50000 Hz and more preferably in a range of 10 Hz to 1000
Hz.
Moreover, in order to shorten the exposure treatment time, the
frequency of the laser is more preferably 10 Hz or greater and most
preferably 100 Hz or greater. In order to improve aligning accuracy
at the time of scanning exposure, the frequency of the laser is
more preferably 10000 Hz or less and most preferably 1000 Hz or
less.
When a laser is compared to a mercury lamp, a laser is preferable
in terms that a laser can be more easily focused and a mask for
pattern formation during the exposure process is unnecessary and
this leads to cost reduction.
An exposure device which can be used in the present invention is
not particularly limited, and a Callisto (manufactured by
V-Technology Co., Ltd.), an AEGIS (manufactured by V-Technology
Co., Ltd.), or a DF2200G (manufactured by SCREEN Holdings Co.,
Ltd.) can be exemplified as a commercially available product.
Further, devices other that those described above are suitably
used.
Moreover, irradiation light can be adjusted through a spectral
filter such as a long wavelength cut filter, a short wavelength cut
filter, and a band-pass filter if necessary.
<<(4) Process of Performing Development Using Developer
Containing Organic Solvent to Prepare Mask Pattern>>
After the resist film is exposed by the process (3), development is
performed using a developer containing an organic solvent. The
development is preferably a negative type development. The sp value
of the solvent contained in the developer is preferably less than
19 MPa.sup.1/2 and more preferably 18 MPa.sup.1/2 or less.
As the organic solvent contained in the developer used in the
present invention, a polar solvent such as a ketone-based solvent,
an ester-based solvent, or an amide-based solvent and a
hydrocarbon-based solvent can be used.
Examples of the ketone-based solvent include 1-octanone,
2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl
ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone,
cyclohexanone, methyl cyclohexanone, phenyl acetone, methyl ethyl
ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone,
ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl
naphthyl ketone, isophorone, and propylene carbonate.
Examples of the ester-based solvent include methyl acetate, butyl
acetate, ethyl acetate, isopropyl acetate, pentyl acetate,
isopentyl acetate, amyl acetate, propylene glycol monomethyl ether
acetate, ethylene glycol monoethyl ether acetate, diethylene glycol
monobutyl ether acetate, diethylene glycol monoethyl ether acetate,
ethyl-3-ethoxy propionate, 3-methoxybutyl acetate,
3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate,
butyl formate, propyl formate, ethyl lactate, butyl lactate, and
propyl lactate.
Examples of the amide-based solvent include N-methyl-2-pyrrolidone,
N,N-dimethylacetamide, N,N-dimethylformamide, hexamethyl phosphoric
triamide, and 1,3-dimethyl-2-imidazolidinone.
Examples of the hydrocarbon-based solvent include an aromatic
hydrocarbon-based solvent such as toluene or xylene and an
aliphatic hydrocarbon-based solvent such as pentane, hexane,
octane, or decane.
The above-described solvents may be used alone or in combination of
two or more kinds thereof. In addition, the solvents may be used by
being mixed with solvents other than the solvents described above.
In this case, for the purpose of sufficiently exhibiting the
effects of the present invention, it is preferable that the
moisture content in a whole developer is less than 10% by mass and
more preferable that substantially no moisture is contained. The
term "substantially" here means that the moisture content in a
whole developer is 3% by mass or less and more preferably below the
measurement limit.
That is, the amount of the organic solvent used with respect to an
organic developer is preferable in a range of 90% by mass to 100%
by mass and more preferably in a range of 95% by mass to 100% by
mass with respect to the total amount of the developer.
Particularly, it is preferable that the organic developer is a
developer containing at least one organic solvent selected from a
group consisting of a ketone-based solvent, an ester-based solvent,
and an amide-based solvent.
In addition, the organic developer may contain an appropriate
amount of a basic compound as needed. Examples of the basic
compound are the same as those described above in the section of
the basic compound.
The vapor pressure of the organic developer at 20.degree. C. is
preferably 5 kPa or less, more preferably 3 kPa or less, and
particularly preferably 2 kPa or less. When the vapor pressure of
the organic developer is set to 5 kPa or less, evaporation on a
substrate of the developer or in a developing cup is suppressed,
temperature uniformity in a wafer surface is improved, and thus
dimensional uniformity in the wafer surface is improved.
Specific examples of an organic developer having a vapor pressure
of 5 kPa or less include a ketone-based solvent such as 1-octanone,
2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl
ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone,
methyl cyclohexanone, phenyl acetone, or methyl isobutyl ketone; an
ester-based solvent such as butyl acetate, pentyl acetate,
isopentyl acetate, amyl acetate, propylene glycol monomethyl ether
acetate, ethylene glycol monoethyl ether acetate, diethylene glycol
monobutyl ether acetate, diethylene glycol monoethyl ether acetate,
ethyl-3-ethoxy propionate, 3-methoxybutyl acetate,
3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate,
ethyl lactate, butyl lactate, or propyl lactate; an amide-based
solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, or
N,N-dimethylformamide; an aromatic hydrocarbon-based solvent such
as toluene or xylene; and an aliphatic hydrocarbon-based solvent
such as octane or decane.
Specific examples of an organic developer having a vapor pressure
of 2 kPa or less which is the particularly preferred range include
a ketone-based solvent such as 1-octanone, 2-octanone, 1-nonanone,
2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone,
cyclohexanone, methyl cyclohexanone, or phenyl acetone; an
ester-based solvent such as butyl acetate, amyl acetate, propylene
glycol monomethyl ether acetate, ethylene glycol monoethyl ether
acetate, diethylene glycol monobutyl ether acetate, diethylene
glycol monoethyl ether acetate, ethyl-3-ethoxy propionate,
3-methoxy butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl
lactate, butyl lactate, or propyl lactate; an amide-based solvent
such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, or
N,N-dimethylformamide; an aromatic hydrocarbon-based solvent such
as xylene; and an aliphatic hydrocarbon-based solvent such as
octane or decane.
An appropriate amount of a surfactant can be added to the developer
as needed.
The surfactants described in the section of the water-soluble resin
composition are preferably used as the surfactants although not
particularly limited.
In a case where a surfactant is mixed with the developer, the
content is normally in a range of 0.001% by mass to 5% by mass,
preferably in a range of 0.005% by mass to 2% by mass, and still
more preferably in a range of 0.01% by mass to 0.5% by mass with
respect to the total amount of the developer.
As a developing method, a method of immersing a substrate in a bath
filled with a developer for a certain period of time (dip method);
a method of performing development by raising a developer onto the
surface of a substrate using the surface tension and allowing the
developer to stand still for a certain period of time (paddle
method); a method of spraying a developer on the surface of a
substrate (spray method); and a method of discharging a developer
while a developer discharge nozzle is scanned at a constant rate on
a substrate that rotates at a constant rate (dynamic dispense
method) can be used.
In a case where the various developing methods include a method of
discharging a developer to a resist film from a development nozzle
of a developing device, the discharge pressure (the flow rate per
unit area of the developer to be discharged) of the developer to be
discharged is preferably in a range of 2 mL/sec/mm.sup.2 or less,
more preferably 1.5 mL/sec/mm.sup.2 or less, and still more
preferably 1 mL/sec/mm.sup.2 or less. The lower limit of the flow
rate is not particularly limited, but is preferably 0.2
mL/sec/mm.sup.2 or greater when throughput is considered.
When the discharge pressure of the developer to be discharged is
set to be in the above-described range, defects in a pattern
derived from resist residues after development can be significantly
reduced.
The details of this mechanism is not clear, but it is considered
that the defects can be reduced because the pressure of the
developer being applied to the resist film is decreased and thus
unexpected scraping or collapsing of the resist film and the resist
pattern is suppressed by setting the discharge pressure to be in
the above-described range.
In addition, the discharge pressure (mL/sec/mm.sup.2) of the
developer is a value in a developing nozzle outlet in the
developing device.
Examples of a method of adjusting the discharge pressure of the
developer include a method of adjusting the discharge pressure
using a pump or the like and a method of adjusting and changing the
discharge pressure with a supply from a pressure tank.
Further, after the process of performing development using the
developer containing an organic solvent, a process of stopping
development may be carried out while the organic solvent is
replaced by another solvent.
<<(5) Process of Removing at Least Water-Soluble Resin Film
and Organic Semiconductor of Non-Mask Portion During Etching
Treatment>>
For example, the resist film is developed and a mask pattern 4 is
prepared as illustrated in FIG. 1(C), and then the water-soluble
resin film 3 and the organic semiconductor film 2 of at least a
non-mask portion are removed during the etching treatment as
illustrated in FIG. 1(D). The non-mask portion indicates a portion
which is not exposed to light due to a mask when a mask pattern is
prepared by exposing the resist film to light. Hereinafter, a case
where the etching treatment is a dry etching treatment and a case
where the etching treatment is a wet etching treatment will be
described.
<<Dry Etching Treatment>>
Specifically, during the dry etching treatment, the resist pattern
is used as an etching mask and at least the water-soluble resin
film and the organic semiconductor are dry-etched. Typical examples
of the dry etching include methods described in JP1984-126506A
(JP-559-126506A), JP1984-46628A (JP-557-46628A), JP1983-9108A
(JP-558-9108A), JP1983-2809A (JP-558-2809A), JP1982-148706A
(JP-557-148706A), and JP1986-41102A (JP-561-41102A).
It is preferable that the dry etching is performed by following an
embodiment from viewpoints of forming a pattern section to have a
shape close to a rectangular shape and further reducing damage to
the organic semiconductor.
An embodiment which includes a first step of etching that performs
etching up to a region (depth) to which the organic semiconductor
is not exposed using a mixed gas of fluorine-based gas and oxygen
gas (O.sub.2), a second step of etching that performs etching
preferably close to a region (depth) to which the organic
semiconductor is exposed using mixed gas of nitrogen gas (N2) and
oxygen gas (O2) after the first step of etching, and overetching
performed after the organic semiconductor is exposed is preferable.
Hereinafter, a specific method of the dry etching, the first step
of etching, the second step of etching and the overetching will be
described.
The dry etching is performed by acquiring etching conditions in
advance using the following method.
(1) An etching rate (nm/min) in the first step of etching and an
etching rate (nm/min) in the second step of etching are
respectively calculated. (2) The etching time over which a desired
thickness is obtained by the first step of etching and the etching
time over which a desired thickness is obtained by the second step
of etching are respectively calculated. (3) The first step of
etching is performed according to the etching time calculated in
the process (2) described above. (4) The second step of etching is
performed according to the etching time calculated in the process
(2) described above. Alternatively, the etching time is determined
by end point detection and then the second step of etching may be
performed according to the determined etching time. (5) The
overetching time with respect to the total time of (3) and (4)
described above is calculated and the overetching is performed.
It is preferable that the mixed gas used in the first step of the
etching process contains fluorine-based gas and oxygen gas
(O.sub.2) from a viewpoint of processing an organic material, which
is a film to be etched, to have a rectangular shape. Moreover, in
the first step of the etching process, damage to the organic
semiconductor can be avoided by performing etching up to a region
to which the organic semiconductor is not exposed. In addition, it
is preferable that the etching treatment is performed using a mixed
gas of nitrogen gas and oxygen gas in the second step of the
etching process and the overetching process from a viewpoint that
the etching is performed up to the region to which the organic
semiconductor is not exposed using a mixed gas of fluorine-based
gas and oxygen gas during the first step of the etching process and
thus damage to the organic semiconductor is avoided.
It is important that the ratio of the etching amount during the
first step of the etching process to the etching amount during the
second step of the etching process is determined such that the
rectangular properties due to the etching treatment during the
first step of the etching process are not degraded. In addition,
the ratio of the etching amount in the second step of the etching
process to the total etching amount (the total amount of the
etching amount in the first step of the etching process and the
etching amount in the second step of the etching process) is
preferably greater than 0% and equal to or less than 50% and more
preferably in a range of 10% to 20%. The etching amount indicates
the amount calculated from a difference between the film thickness
of a remaining film to be etched and the film thickness before
etching.
In addition, it is preferable that the etching includes the
overetching process. It is preferable that the overetching
treatment is performed by setting an overetching ratio. Further, it
is preferable that the overetching ratio is calculated from the
time for the etching treatment which is carried out for the first
time. The overetching ratio can be arbitrarily set, but the
overetching ratio is preferably 30% or less, more preferably 5% to
25%, and particularly preferably 10% to 15% of the etching
treatment time in this etching process from a viewpoint of
maintaining etching resistance of a photoresist and rectangular
properties of a pattern to be etched.
<<Wet Etching Treatment>>
Specifically, in wet etching, at least the water-soluble resin film
and the organic semiconductor are wet-etched using a resist pattern
as an etching mask.
As the wet etching process, a dipping type etching method of
performing etching by immersing a substrate in an etching solution;
a shower type etching method of performing etching by exposing a
substrate to a shower-like etching solution; a spray type etching
method of spraying an etching solution onto a substrate; and the
like are known, but a shower type etching method and a spray type
etching method are preferable from a viewpoint of performing
processing on an organic material, which is a film to be etched, to
have a rectangular shape.
Moreover, it is preferable that etching is performed by following
an embodiment from viewpoints of forming a pattern section to have
a shape closer to a rectangular shape and further reducing damage
to the organic semiconductor.
An embodiment which includes a first step of etching that performs
etching of the water-soluble resin film using at least one of
primary alcohols and secondary alcohols and a second step of
etching that is performed after the organic semiconductor is
exposed using a liquid dissolving the organic semiconductor after
the first step of etching is preferable.
Examples of the primary alcohols and the secondary alcohols are the
same as the primary alcohols and the secondary alcohols described
in the water-soluble resin composition that forms the water-soluble
resin film described above.
Hereinafter, a specific method of wet etching, the first step of
etching, and the second step of etching will be described.
The wet etching is performed by acquiring etching conditions in
advance using the following method.
(1) An etching rate (nm/min) in the first step of etching and an
etching rate (nm/min) in the second step of etching are
respectively calculated. (2) The etching time over which a desired
thickness is obtained by the first step of etching and the etching
time for which a desired thickness is obtained by the second step
of etching are respectively calculated. (3) The first step of
etching is performed according to the etching time calculated in
the process (2) described above. (4) The second step of etching is
performed according to the etching time calculated in the process
(2) described above.
The etching is performed up to a region to which the organic
semiconductor is exposed during the first step of the etching
process and thus the second step of etching becomes possible.
Further, in the second step of etching process, it is preferable
that the etching treatment is performed using a solvent that
dissolves the organic semiconductor after etching is performed up
to a region to which the organic semiconductor is exposed by at
least one of the primary alcohols and the secondary alcohols in the
first step of the etching process.
It is important that the ratio of the etching amount during the
first step of the etching process to the etching amount during the
second step of the etching process is determined such that the
rectangular properties due to the etching treatment during the
first step of the etching process are not degraded. In addition,
the ratio of the etching amount in the second step of the etching
process to the total etching amount (the total amount of the
etching amount in the first step of the etching process and the
etching amount in the second step of the etching process) is
preferably greater than 0% and equal to or less than 50% and more
preferably in a range of 10% to 20%. The etching amount indicates
the amount calculated from a difference between the film thickness
of a remaining film to be etched and the film thickness before
etching.
In a case of the wet etching, since the resist pattern remains on
the mask pattern formed of a water-soluble resin, it is necessary
to perform peeling off of the resist pattern.
As the organic solvent containing a peeling solution used in the
present invention, a polar solvent such as a ketone-based solvent,
an amide-based solvent, an alcohol-based solvent, an ether-based
solvent, and a nitrile-based solvent can be used.
As the ketone-based solvent, acetone, methyl ethyl ketone,
cyclohexanone, methylcyclohexanone, or acetyl acetone can be
used.
As the amide-based solvent, N-methyl-2-pyrrolidone,
N,N-dimethylacetamide, N,N-dimethylformamide, hexamethyl phosphoric
triamide, or 1,3-dimethyl-2-imidazolidinone can be used.
As the alcohol-based solvent, a primary alcohol-based solvent such
as methanol, ethanol, or 3-methyl-1-butanol, or a secondary
alcohol-based solvent such as 2-propanol, 4-methyl-2-pentanol, or
3-methoxy-1-butanol can be used.
As the ether-based solvent, propylene glycol monomethyl ether or
tetrahydrofuran can be used.
As the nitrile-based solvent, acetonitrile can be used.
The organic solvent contained in the peeling solution may be used
alone or two or more kinds thereof. In addition, the organic
solvent may be used by being mixed with a solvent other than the
solvents described above.
Particularly, it is preferable that the peeling solution contains
at least one organic solvent selected from a group consisting of a
ketone-based solvent, an alcohol-based solvent, an ether-based
solvent, and a nitrile-based solvent.
<<(6) Process of Dissolving and Removing Water-Soluble Resin
Film Using Water>>
After etching, the water-soluble resin film is removed using water.
In this manner, for example, a substrate in which the organic
semiconductor film 2 is patterned is obtained as illustrated in
FIG. 1(E).
As a method of removing the water-soluble resin film using water, a
method of spraying cleaning water to the resist pattern from a
spray type or shower type spray nozzle and removing the
water-soluble resin film is exemplified. As the cleaning water,
pure water can be preferably used. Further, as the spray nozzle, a
spray nozzle in which the entire support is included in the spray
range or a spray nozzle which is a movable spray nozzle and in
which the entire support is included in the movable range can be
exemplified. In a case where the injection nozzle is a movable type
nozzle, the resist pattern can be more effectively removed by
moving the injection nozzle from the center portion of the support
to the end portion of the support two or more times during the
process of removing the water-soluble resin film and spraying
cleaning water.
It is preferable that a process of drying or the like is performed
after water is removed. The drying temperature is preferably in a
range of 80.degree. C. to 120.degree. C.
INDUSTRIAL APPLICABILITY
The present invention can be used for production of an electronic
device using an organic semiconductor. Here, the electronic device
means a device that includes a semiconductor and two or more
electrodes and controls a current flowing between the electrodes
and a voltage to be generated using electricity, light, magnetism,
and chemical substances or a device that generates light, an
electric field, or a magnetic field using applied voltage or a
current. Examples thereof include an organic photoelectric
conversion element, an organic field effect transistor, an organic
electroluminescence light emitting device, a gas sensor, an organic
rectifying element, an organic inverter, and an information
recording element. The organic photoelectric conversion element can
be used for a light sensor and energy conversion (solar cell).
Among these, an organic field effect transistor, an organic
photoelectric conversion element, or an organic electroluminescence
light emitting device is preferable, an organic field effect
transistor or an organic photoelectric conversion element is more
preferable, and an organic field effect transistor is particularly
preferable.
EXAMPLES
Hereinafter, the present invention will be more specifically
described with reference to examples, but the present invention is
not limited to the examples described below within the range not
departing from the scope of the present invention. Further, "%" and
"parts" are on a mass basis unless otherwise noted.
Abbreviations of respective compounds respectively indicate the
following compounds. BzMA: benzyl methacrylate (manufactured by
Wako Pure Chemical Industries, Ltd.) t-BuMA: tert-butyl
methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MA: methacrylic acid (manufactured by Wako Pure Chemical
Industries, Ltd.) PMA: phenyl methacrylate (manufactured by Wako
Pure Chemical Industries, Ltd.) THFMA: 2-tetrahydrofuranyl
methacrylate (synthetic product) TFFAA: 2-tetrahydrofuranyl
acrylate (synthetic product) MTHFMA: 5-methyl-2-tetrahydrofuranyl
methacrylate (synthetic product) THPMA: 2-tetrahydropyranyl
methacrylate (synthetic product) THPAA: 2-tetrahydropyranyl
acrylate (synthetic product) PEES: p-ethoxyethoxystyrene V-601:
dimethyl 2,2-azobis(2-methylpropionate) (manufactured by Wako Pure
Chemical Industries, Ltd.) PGMEA: methoxypropyl acetate
(manufactured by Daicel Corporation)
Synthesis Example 1
Synthesis of THFMA
50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2% by mole)
of camphorsulfonic acid were mixed with each other in a
three-necked flask and then the mixture was cooled to 15.degree. C.
41.00 g (0.585 mol) of 2,3-dihydrofuran was added dropwise to the
solution. A saturated sodium bicarbonate solution (500 mL) was
added dropwise to the reaction solution, and the resultant was
extracted with ethyl acetate (500 mL) and dried over magnesium
sulfate. The insoluble matter was concentrated at 40.degree. C. or
lower under a reduced pressure after filtration and a colorless oil
residue was distilled off under reduced pressure, thereby obtaining
73.02 g of THFMA.
Synthesis Example 2
Synthesis of THFAA
42.16 g (0.585 mol) of acrylic acid and 0.27 g (0.2% by mole) of
camphorsulfonic acid were mixed with each other in a three-necked
flask and then the mixture was cooled to 15.degree. C. 41.00 g
(0.585 mol) of 2,3-dihydrofuran was added dropwise to the solution.
A saturated sodium bicarbonate solution (500 mL) was added dropwise
to the reaction solution, and the resultant was extracted with
ethyl acetate (500 mL) and dried over magnesium sulfate. The
insoluble matter was concentrated at 40.degree. C. or lower under a
reduced pressure after filtration and a colorless oil residue was
distilled off under reduced pressure, thereby obtaining 62.18 g of
THFAA.
Synthesis Example 3
Synthesis of MTHFMA
50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2% by mole)
of camphorsulfonic acid were mixed with each other in a
three-necked flask and then the mixture was cooled to 15.degree. C.
49.21 g (0.585 mol) of 5-methyl-2,3-dihydrofuran was added dropwise
to the solution. A saturated sodium bicarbonate solution (500 mL)
was added dropwise to the reaction solution, and the resultant was
extracted with ethyl acetate (500 mL) and dried over magnesium
sulfate. The insoluble matter was concentrated at 40.degree. C. or
lower under a reduced pressure after filtration and a colorless oil
residue was distilled off under reduced pressure, thereby obtaining
66.70 g of MTHFMA.
Synthesis Example 4
Synthesis of THPMA
50.33 g (0.585 mol) of methacrylic acid and 0.27 g (0.2% by mole)
of camphorsulfonic acid were mixed with each other in a
three-necked flask and then the mixture was cooled to 15.degree. C.
49.21 g (0.585 mol) of 3,4-dihydrofuran was added dropwise to the
solution. A saturated sodium bicarbonate solution (500 mL) was
added dropwise to the reaction solution, and the resultant was
extracted with ethyl acetate (500 mL) and dried over magnesium
sulfate. The insoluble matter was concentrated at 40.degree. C. or
lower under a reduced pressure after filtration and a colorless oil
residue was distilled off under reduced pressure, thereby obtaining
68.64 g of THPMA.
Synthesis Example 5
Synthesis of THPAA
42.16 g (0.585 mol) of acrylic acid and 0.27 g (0.2% by mole) of
camphorsulfonic acid were mixed with each other in a three-necked
flask and then the mixture was cooled to 15.degree. C. 49.21 g
(0.585 mol) of 3,4-dihydrofuran was added dropwise to the solution.
A saturated sodium bicarbonate solution (500 mL) was added dropwise
to the reaction solution, and the resultant was extracted by ethyl
acetate (500 mL) and dried over magnesium sulfate. The insoluble
matter was concentrated at 40.degree. C. or lower under a reduced
pressure after filtration and a colorless oil residue was distilled
off under reduced pressure, thereby obtaining 63.13 g of THPAA.
Synthesis Example 6
Synthesis of Specific Resin C1
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (9.25 g), THFMA (11.71 g), t-BuMA (3.20 g), and
V-601 (0.895 g, 2.59% by mole with respect to monomers) were
dissolved in the PGMEA (18.12 g) and the mixture was added dropwise
to a solution over 2 hours. After dropwise addition, the solution
was stirred for 4 hours and the reaction finished. In this manner,
a specific resin C1 was obtained. The weight average molecular
weight was 15000.
Synthesis Example 7
Synthesis of Specific Resin C2
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (9.25 g), THFAA (10.66 g), t-BuMA (3.20 g), and
V-601 (0.895 g, 2.59% by mole with respect to monomers) were
dissolved in the PGMEA (18.12 g) and the mixture was added dropwise
to a solution over 2 hours. After dropwise addition, the solution
was stirred for 4 hours and the reaction finished. In this manner,
a specific resin C2 was obtained. The weight average molecular
weight was 14000.
Synthesis Example 8
Synthesis of Specific Resin C3
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (9.25 g), MTHFAA (11.71 g), t-BuMA (3.20 g), and
V-601 (0.895 g, 2.59% by mole with respect to monomers) were
dissolved in the PGMEA (18.12 g) and the mixture was added dropwise
to a solution over 2 hours. After dropwise addition, the solution
was stirred for 4 hours and the reaction finished. In this manner,
a specific resin C3 was obtained. The weight average molecular
weight was 15000.
Synthesis Example 9
Synthesis of Specific Resin C4
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (9.25 g), THPMA (12.76 g), t-BuMA (3.20 g), and
V-601 (0.895 g, 2.59% by mole with respect to monomers) were
dissolved in the PGMEA (18.12 g) and the mixture was added dropwise
to a solution over 2 hours. After dropwise addition, the solution
was stirred for 4 hours and the reaction finished. In this manner,
a specific resin C4 was obtained. The weight average molecular
weight was 16000.
Synthesis Example 10
Synthesis of Specific Resin C5
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (9.25 g), THPMA (11.71 g), t-BuMA (3.20 g), and
V-601 (0.895 g, 2.59% by mole with respect to monomers) were
dissolved in in PGMEA (18.12 g) and the mixture was added dropwise
to a solution over 2 hours. After dropwise addition, the solution
was stirred for 4 hours and the reaction finished. In this manner,
a specific resin C5 was obtained. The weight average molecular
weight was 16000.
Synthesis Example 11
Synthesis of Specific Resin C6
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (14.53 g), t-BuMA (9.59 g), and V-601 (0.895 g,
2.59% by mole with respect to monomers) were dissolved in the PGMEA
(18.12 g) and the mixture was added dropwise to a solution over 2
hours. After dropwise addition, the solution was stirred for 4
hours and the reaction finished. In this manner, a specific resin
C6 was obtained. The weight average molecular weight was 16000.
Synthesis Example 12
Synthesis of Specific Resin C7
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (9.25 g), PEES (14.43 g), t-BuMA (3.20 g), and
V-601 (0.895 g, 2.59% by mole with respect to monomers) were
dissolved in the PGMEA (18.12 g) and the mixture was added dropwise
to a solution over 2 hours. After dropwise addition, the solution
was stirred for 4 hours and the reaction finished. In this manner,
a specific resin C7 was obtained. The weight average molecular
weight was 16000.
Synthesis Example 13
Synthesis of Specific Resin C8
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (14.54 g), PEES (12.99 g), and V-601 (0.895 g,
2.59% by mole with respect to monomers) were dissolved in the PGMEA
(18.12 g) and the mixture was added dropwise to a solution over 2
hours. After dropwise addition, the solution was stirred for 4
hours and the reaction finished. In this manner, a specific resin
C8 was obtained. The weight average molecular weight was 16000.
Synthesis Example 14
Synthesis of Photoacid Generator D1
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g)
were added to a suspension of 2-naphthol (10 g) and chlorobenzene
(30 mL) and the mixed solution was heated to 40.degree. C. and
reacted for 2 hours. Under ice-cold conditions, a 4N-HCl aqueous
solution (60 mL) was added dropwise to the reaction solution and
ethyl acetate (50 mL) was added to the solution for liquid
separation. Potassium carbonate (19.2 g) was added to an organic
layer, the mixture was reacted at 40.degree. C. for 1 hour, a
2N-HCl aqueous solution (60 mL) was added for liquid separation,
the organic layer was concentrated, and crystals were reslurried
with diisopropyl ether (10 mL), filtered off, and dried, thereby
obtaining a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass % hydroxylamine aqueous solution
(8.0 g) were added to a suspension of the obtained ketone compound
(3.0 g) and methanol (30 mL), and the solution was heated and
refluxed. After the solution was cooled, water (50 mL) was added
thereto, and deposited crystals were filtered off and then washed
with cold methanol and dried, thereby obtaining an oxime compound
(2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20
mL), trimethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g)
were added thereto under ice-cold conditions, the temperature was
increased to room temperature, and the solution was reacted for 1
hour. Water (50 mL) was added to the reaction solution and the
deposited crystals were filtered off, reslurried with methanol (20
mL), filtered off, and dried, thereby obtaining D1 (2.3 g).
Further, .sup.1H-NMR spectrum (300 MHz, CNCl.sub.3) of D1 was
.delta.=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6
(dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4
(s, 3H), and 1.7 (d, 3H).
Synthesis Example 15
Synthesis of Photoacid Generator D2
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g)
were added to a suspension of 2-naphthol (10 g) and chlorobenzene
(30 mL) and the mixed solution was heated to 40.degree. C. and
reacted for 2 hours. Under ice-cold conditions, a 4N-HCl aqueous
solution (60 mL) was added dropwise to the reaction solution and
ethyl acetate (50 mL) was added to the solution for liquid
separation. Potassium carbonate (19.2 g) was added to an organic
layer, the mixture was reacted at 40.degree. C. for 1 hour, a
2N-HCl aqueous solution (60 mL) was added for liquid separation,
the organic layer was concentrated, and crystals were reslurried
with diisopropyl ether (10 mL), filtered off, and dried, thereby
obtaining a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass % hydroxylamine aqueous solution
(8.0 g) were added to a suspension of the obtained ketone compound
(3.0 g) and methanol (30 mL), and the solution was heated and
refluxed. After the solution was cooled, water (50 mL) was added
thereto, and deposited crystals were filtered off and then washed
with cold methanol and dried, thereby obtaining an oxime compound
(2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20
mL), trimethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g)
were added thereto under ice-cold conditions, the temperature was
increased to room temperature, and the solution was reacted for 1
hour. Water (50 mL) was added to the reaction solution and the
deposited crystals were filtered off, reslurried with methanol (20
mL), filtered off, and dried, thereby obtaining D2 (2.3 g).
Further, .sup.1H-NMR spectrum (300 MHz, CDCl.sub.3) of D2 was
.delta.=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6
(dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d. 1H), 5.6 (q, 1H), 2.4
(s, 3H), and 1.7 (d, 3H).
Synthesis Example 16
Synthesis of Photoacid Generator D3
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g)
were added to a suspension of 2-naphthol (10 g) and chlorobenzene
(30 mL) and the mixed solution was heated to 40.degree. C. and
reacted for 2 hours. Under ice-cold conditions, a 4N-HCl aqueous
solution (60 mL) was added dropwise to the reaction solution and
ethyl acetate (50 mL) was added to the solution for liquid
separation. Potassium carbonate (19.2 g) was added to an organic
layer, the mixture was reacted at 40.degree. C. for 1 hour, a
2N-HCl aqueous solution (60 mL) was added for liquid separation,
the organic layer was concentrated, and crystals were reslurried
with diisopropyl ether (10 mL), filtered off, and dried, thereby
obtaining a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass % hydroxylamine aqueous solution
(8.0 g) were added to a suspension of the obtained ketone compound
(3.0 g) and methanol (30 mL), and the solution was heated and
refluxed. After the solution was cooled, water (50 mL) was added
thereto, and deposited crystals were filtered off and then washed
with cold methanol and dried, thereby obtaining an oxime compound
(2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20
mL), trimethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g)
were added thereto under ice-cold conditions, the temperature was
increased to room temperature, and the solution was reacted for 1
hour. Water (50 mL) was added to the reaction solution and the
deposited crystals were filtered off, reslurried with methanol (20
mL), filtered off, and dried, thereby obtaining D3 (2.3 g).
Further, .sup.1H-NMR spectrum (300 MHz, CNCl.sub.3) of D3 was
.delta.=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6
(dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d. 1H), 5.6 (q, 1H), 2.4
(s, 3H), and 1.7 (d, 3H).
(1) Preparation of Water-Soluble Resin Composition and
Photosensitive Resin Composition
Respective components listed in table below were mixed to obtain a
uniform solution, the solution was filtered using a
polytetrafluoroethylene filter having a pore size of 0.1 .mu.m, and
then water-soluble resin compositions and photosensitive resin
compositions of Examples 1 to 21 and Comparative Examples 1 to 12
were respectively prepared.
TABLE-US-00001 TABLE 1 Chemically amplified photosensitive resin
composition Decom- Water-soluble resin composition position Water-
Specific Photoacid rate of Basic soluble resin Surfactant Solvent
resin generator photoacid compound Surfa- ctant Solvent Type Parts
Type Parts Type Parts Type Parts Type Parts generator Type Par- ts
Type Parts Type Parts Example 1 A1 9.9 B1 0.1 Water 90 C1 14.75 D1
0.16 A E1 0.05 F1 0.05 PGMEA - 85.00 Example 2 A1 9.9 B1 0.1 Water
90 C1 14.75 D2 0.16 A E1 0.05 F1 0.05 PGMEA - 85.00 Example 3 A1
9.9 B1 0.1 Water 90 C1 14.75 D3 0.16 A E1 0.05 F1 0.05 PGMEA -
85.00 Example 4 A1 9.9 B1 0.1 Water 90 C2 14.75 D1 0.16 A E1 0.05
F1 0.05 PGMEA - 85.00 Example 5 A1 9.9 B1 0.1 Water 90 C2 14.75 D2
0.16 A E1 0.05 F1 0.05 PGMEA - 85.00 Example 6 A1 9.9 B1 0.1 Water
90 C2 14.75 D3 0.16 A E1 0.05 F1 0.05 PGMEA - 85.00 Example 7 A1
9.9 B1 0.1 Water 90 C3 14.75 D1 0.16 A E1 0.05 F1 0.05 PGMEA -
85.00 Example 8 A1 9.9 B1 0.1 Water 90 C3 14.75 D2 0.16 A E1 0.05
F1 0.05 PGMEA - 85.00 Example 9 A1 9.9 B1 0.1 Water 90 C3 14.75 D3
0.16 A E1 0.05 F1 0.05 PGMEA - 85.00 Example 10 A1 9.9 B1 0.1 Water
90 C4 14.75 D1 0.16 A E1 0.05 F1 0.05 PGMEA- 85.00 Example 11 A1
9.9 B1 0.1 Water 90 C4 14.75 D2 0.16 A E1 0.05 F1 0.05 PGMEA- 85.00
Example 12 A1 9.9 B1 0.1 Water 90 C4 14.75 D3 0.16 A E1 0.05 F1
0.05 PGMEA- 85.00 Example 13 A1 9.9 B1 0.1 Water 90 C5 14.75 D1
0.16 A E1 0.05 F1 0.05 PGMEA- 85.00 Example 14 A1 9.9 B1 0.1 Water
90 C5 14.75 D2 0.16 A E1 0.05 F1 0.05 PGMEA- 85.00 Example 15 A1
9.9 B1 0.1 Water 90 C5 14.75 D3 0.16 A E1 0.05 F1 0.05 PGMEA- 85.00
Example 16 A1 9.9 B1 0.1 Water 90 C6 14.75 D1 0.16 A E1 0.05 F1
0.05 PGMEA- 85.00 Example 17 A1 9.9 B1 0.1 Water 90 C7 14.75 D1
0.16 A E1 0.05 F1 0.05 PGMEA- 85.00 Example 18 A1 9.9 B1 0.1 Water
90 C8 14.75 D1 0.16 A E1 0.05 F1 0.05 PGMEA- 85.00 Example 19 A2
9.9 B1 0.1 Water 90 C1 14.75 D1 0.16 A E1 0.05 F1 0.05 PGMEA- 85.00
Example 20 A3 9.9 B1 0.1 Water 90 C1 14.75 D1 0.16 A E1 0.05 F1
0.05 PGMEA- 85.00 Example 21 A4 9.9 B1 0.1 Water 90 C1 14.75 D1
0.16 A E1 0.05 F1 0.05 PGMEA- 85.00 Comparative A1 9.9 B1 0.1 Water
90 C1 14.75 D4 0.16 B E1 0.05 F1 0.05 PGME- A 85.00 Example 1
Comparative A1 9.9 B1 0.1 Water 90 C1 14.75 D5 0.16 C E1 0.05 F1
0.05 PGME- A 85.00 Example 2 Comparative A1 9.9 B1 0.1 Water 90 C1
14.75 D6 0.16 C E1 0.05 F1 0.05 PGME- A 85.00 Example 3 Comparative
A1 9.9 B1 0.1 Water 90 C6 14.75 D4 0.16 B E1 0.05 F1 0.05 PGME- A
85.00 Example 4 Comparative A1 9.9 B1 0.1 Water 90 C6 14.75 D5 0.16
C E1 0.05 F1 0.05 PGME- A 85.00 Example 5 Comparative A1 9.9 B1 0.1
Water 90 C6 14.75 D6 0.16 C E1 0.05 F1 0.05 PGME- A 85.00 Example 6
Comparative A1 9.9 B1 0.1 Water 90 C7 14.75 D4 0.16 B E1 0.05 F1
0.05 PGME- A 85.00 Example 7 Comparative A1 9.9 B1 0.1 Water 90 C7
14.75 D5 0.16 C E1 0.05 F1 0.05 PGME- A 85.00 Example 8 Comparative
A1 9.9 B1 0.1 Water 90 C7 14.75 D6 0.16 C E1 0.05 F1 0.05 PGME- A
85.00 Example 9 Comparative A1 9.9 B1 0.1 Water 90 C8 14.75 D4 0.16
B E1 0.05 F1 0.05 PGME- A 85.00 Example 10 Comparative A1 9.9 B1
0.1 Water 90 C8 14.75 D5 0.16 C E1 0.05 F1 0.05 PGME- A 85.00
Example 11 Comparative A1 9.9 B1 0.1 Water 90 C8 14.75 D6 0.16 C E1
0.05 F1 0.05 PGME- A 85.00 Example 12
Abbreviations in Table 1 are as follows.
A1: polyvinyl pyrrolidone (Pitts call K-30, manufactured by DKS
Co., Ltd., sp value: 22.5 (MPa).sup.1/2)
A2: polyvinyl alcohol (PXP-05, manufactured by JAPAN VAM &
POVAL CO., LTD., sp value: 25.8 (MPa).sup.1/2)
A3: pullulan (manufactured by Hayashibara Co., Ltd., sp value: 27.8
(MPa).sup.1/2)
A4: methyl cellulose (Metolose SM-4, manufactured by Shin-Etsu
Chemical Co., Ltd., sp value: 35.6 (MPa).sup.1/2)
B1: acetylenol E00 (manufactured by Kawaken Fine Chemical Co.,
Ltd.)
D1: (the following structure, synthetic product)
D2: (the following structure, synthetic product)
D3: (the following structure, synthetic product)
D4: WPAG-336 (the following structure, manufactured by Wako Pure
Chemical Industries, Ltd.)
D5: WPAG-443 (the following structure, manufactured by Wako Pure
Chemical Industries, Ltd.)
D6: MBZ-101 (the following structure, manufactured by Midori Kagaku
Co., Ltd.)
E1: cyclohexyl morpholinoethyl thiourea (the following structure,
manufactured by Inabata & Co., Ltd.)
F1: PF-6320 (the following structure, manufactured by OMNOVA
Solutions Inc.)
##STR00092##
(2) Preparation of Organic Semiconductor Substrate
An organic semiconductor film was formed by spin-coating a glass
substrate having dimensions of 5 cm.sup.2 with an organic
semiconductor coating solution formed of a composition described
below and drying the glass substrate at 130.degree. C. for 10
minutes. The film thickness was 150 nm.
Composition of organic semiconductor coating solution:
TABLE-US-00002 P3HT (manufactured by Sigma-Aldrich Co., LLC.) 10%
by mass PCBM (manufactured by Sigma-Aldrich Co., LLC.) 10% by mass
Chloroform (manufactured by Wako Pure Chemical 80% by mass
Industries, Ltd.)
(3) Process of Coating Substrate with Water-Soluble Resin
Composition
A water-soluble resin film was formed by spin-coating the organic
semiconductor film formed on the substrate with a water-soluble
resin composition formed of a composition listed in the table above
and drying the substrate at 100.degree. C. for 1 minute. The film
thickness was 320 nm.
(4) Process of Preparing Mask Pattern of Resin on Water-Soluble
Resin Film
The formed water-soluble resin film was spin-coated with a
chemically amplified photosensitive resin composition formed of a
composition listed in the table above and dried at 100.degree. C.
for 1 minute. The film thickness was 700 nm. Next, the film was
exposed to light under the condition of 135 mJ/cm.sup.2 using an
i-line a parallel light exposure device. Subsequently, the film was
heated at 100.degree. C. for 1 minute and developed using butyl
acetate, thereby obtaining a mask pattern.
(5) Process of Removing Water-Soluble Resin and Organic
Semiconductor of Non-Mask Portion by Performing Dry Etching
The water-soluble resin film of a non-mask pattern portion and the
organic semiconductor film of the non-mask pattern portion were
removed by performing dry etching on the substrate under the
following conditions.
Gas: CF.sub.4 (flow rate: 200 mL/min), Ar (flow rate: 800 mL/min),
O.sub.2 (flow rate: 50 mL/min)
Source power: 800 W
Wafer bias: 600 W
Antenna bias: 100 W
ESC voltage: 400 V
Time: 60 sec
(6) Process of Dissolving Remaining Water-Soluble Resin in Water
and Removing the Same
The obtained substrate was washed with water, a pattern formed of
the water-soluble resin film was removed, the substrate was heated
at 100.degree. C. for 10 minutes, moisture remaining on the organic
semiconductor film was removed, and the film was dried so that the
damage during the process was repaired, thereby obtaining a
substrate on which the organic semiconductor film was
patterned.
(7) Evaluation
[In-Plane Uniformity of Water-Soluble Resin Film]
The in-plane uniformity of the water-soluble resin film, before the
process of preparing the mask pattern of a resin on the
water-soluble resin film was carried out was measured.
Specifically, in the film thickness of the water-soluble resin
film, the film thicknesses at a total of 100 places from which 2 mm
of the outermost peripheral portion was removed were evaluated
using a reflecting spectrographic film thickness meter. The
evaluation was performed in three stages based on the following
criteria using a coefficient of variation CV (=standard deviation
of film thicknesses/average value of film thicknesses).
A: CV<0.01
B: 0.01.ltoreq.CV<0.04
C: 0.04.ltoreq.CV
[Decomposition Rate of Photoacid Generator when Exposed to Light
Under a Condition of 100 mJ/Cm.sup.2 or Greater at a Wavelength of
365 nm]
A silicon wafer was coated with a chemically amplified
photosensitive resin composition having a film thickness of 700 nm
and heated at 100.degree. C. for 1 minute. Subsequently, the
substrate exposed to light under the condition of 100 mJ/cm.sup.2
at a wavelength of 365 nm and heated at 100.degree. C. for 1 minute
was immersed in a mixture of methanol and THF (mass ratio: 50/50)
for 10 minutes while ultrasonic waves were applied to the solution.
The decomposition rate of the photoacid generator was calculated
using the following formula by analyzing an extract with HPLC and
evaluation was performed based on the following criteria.
Decomposition rate (%)=Amount of decomposition product (mol)/Feed
amount (mol).times.100
A: 80% by mole or greater of the photoacid generator was
decomposed.
B: 40% by mole to less than 80% by mole of the photoacid generator
was decomposed.
C: Less than 40% by mole of the photoacid generator was
decomposed.
[Pattern Shape of Resist Film]
The taper angle of the chemically amplified photosensitive resin
composition was evaluated based on the following criteria by
performing section observation on the pattern of the chemically
amplified photosensitive resin composition, which was formed by a
contact aligner, using a scanning electron microscope.
A: The taper angle of the resin pattern in a 1 .mu.m L/S pattern
was 80.degree. or greater.
B: The residual film ratio of the resin pattern in a 1 .mu.m L/S
pattern was lower than 80.degree..
C: Patterning was impossible.
[Pattern Shape of Organic Semiconductor Film]
The line width of the organic semiconductor was evaluated based on
the following criteria by performing observation on the pattern of
the organic semiconductor, after dry etching was performed and the
water-soluble resin film was removed, using a scanning electron
microscope.
A: The line-width of the organic semiconductor in the 1 .mu.m L/S
pattern of the chemically amplified photosensitive resin
composition was 0.8 .mu.m or greater.
B: The line-width of the organic semiconductor in the 1 .mu.m L/S
pattern of the chemically amplified photosensitive resin
composition was less than 0.8 .mu.m.
C: Patterning was impossible.
TABLE-US-00003 TABLE 2 Chemically amplified photosensitive In-plane
resin composition uniformity Water- Specific Photoacid of water-
Pattern shape soluble resin generator soluble Pattern shape of
organic semi- resin film Type Type resin film of resist film
conductor film Example 1 A1 C1 D1 A A A Example 2 A1 C1 D2 A A A
Example 3 A1 C1 D3 A A A Example 4 A1 C2 D1 A A A Example 5 A1 C2
D2 A A A Example 6 A1 C2 D3 A A A Example 7 A1 C3 D1 A A A Example
8 A1 C3 D2 A A A Example 9 A1 C3 D3 A A A Example 10 A1 C4 D1 A A A
Example 11 A1 C4 D2 A A A Example 12 A1 C4 D3 A A A Example 13 A1
C5 D1 A A A Example 14 A1 C5 D2 A A A Example 15 A1 C5 D3 A A A
Example 16 A1 C6 D1 A B B Example 17 A1 C7 D1 A B B Example 18 A1
C8 D1 A B B Example 19 A2 C1 D1 B A B Example 20 A3 C1 D1 B A B
Example 21 A4 C1 D1 B B B Comparative A1 C1 D4 A B C Example 1
Comparative A1 C1 D5 A B C Example 2 Comparative A1 C1 D6 A B C
Example 3 Comparative A1 C6 D4 A C C Example 4 Comparative A1 C6 D5
A C C Example 5 Comparative A1 C6 D6 A C C Example 6 Comparative A1
C7 D4 A C C Example 7 Comparative A1 C7 D5 A C C Example 8
Comparative A1 C7 D6 A C C Example 9 Comparative A1 C8 D4 A C C
Example 10 Comparative A1 C8 D5 A C C Example 11 Comparative A1 C8
D6 A C C Example 12
As listed in the table above, in Examples 1 to 21, the
water-soluble resin film had excellent in-plane uniformity and
excellent pattern forming properties in the resist film.
Accordingly, it could be understood that a fine pattern of the
organic semiconductor was able to be formed. Meanwhile, in
Comparative Examples 1 to 12, the in-plane uniformity and the
pattern forming properties were degraded. For this reason, it could
be understood that it was unlikely that a fine pattern in the
organic semiconductor would be able to be formed.
The same as in Examples and Comparative Examples above was
performed except that the composition of the water-soluble resin
film was changed as described below. It was found that the same
tendencies as those in Examples and Comparative Examples were
exhibited, as the results therefor.
<Composition 1 of Water-Soluble Resin Composition>
TABLE-US-00004 Polyvinyl pyrrolidone (Pitts call K-30, 14.475% by
mass manufactured by DKS Co., Ltd.) Glycerin (manufactured by
Sigma-Aldrich Co., LLC.) 0.45% by mass Acetylenol E00 (manufactured
by Kawaken Fine 0.075% by mass Chemical Co., Ltd.) Water 85% by
mass
<Composition 2 of Water-Soluble Resin Composition>
TABLE-US-00005 Polyvinyl pyrrolidone (Pitts call K-30, manufactured
13.433% by mass by DKS Co., Ltd.) Polyvinyl alcohol (PXP-05,
manufactured by 1.493% by mass JAPAN VAM & POVAL CO., LTD.)
Acetylenol E00 (manufactured by Kawaken Fine 0.075% by mass
Chemical Co., Ltd.) 2-propanol (manufactured by Sigma-Aldrich Co.,
4.25% by mass LLC.) Water 80.75% by mass
The same as in Examples and Comparative Examples above was
performed except that the composition of the organic semiconductor
coating solution was changed as described below. As a result, it
was recognized that the same tendencies as those in Examples and
Comparative Examples were shown.
<Composition 1 of Organic Semiconductor Coating Solution>
TABLE-US-00006 TIPS pentacene (manufactured by Sigma-Aldrich Co.,
5% by mass LLC.) Toluene (manufactured by Sigma-Aldrich Co., LLC.)
95% by mass
<Composition 2 of Organic Semiconductor Coating Solution>
TABLE-US-00007 MEH-PPV (manufactured by Sigma-Aldrich Co., LLC.)
10% by mass Toluene (manufactured by Sigma-Aldrich Co., LLC.) 90%
by mass
<Composition 3 of Organic Semiconductor Coating Solution>
TABLE-US-00008 PEDOT/PSS (manufactured by Sigma-Aldrich Co., 100%
by mass LLC., 1.3% by mass aqueous dispersion liquid)
The same as in Examples and Comparative Examples above was
performed except that wet etching was performed using the following
etching solution in place of dry etching. As a result, it was
recognized that the same tendencies as those in Examples and
Comparative Examples were shown.
<Etching Solution 1 in First Step>
Water 100% by mass
<Etching Solution 1 in Second Step>
Propylene glycol monomethyl ether 100% by mass
<Etching Solution 2 in First Step>
2-propanol 100% by mass
<Etching Solution 2 in Second Step>
Propylene glycol monomethyl ether 100% by mass
<Etching Solution 3 in First Step>
Water 100% by mass
<Etching Solution 3 in Second Step>
3-methyl-1-butanol 100% by mass
The water-soluble resin film of a non-mask pattern portion and the
organic semiconductor film of the non-mask pattern portion were
removed by performing wet etching on the substrate under the
following conditions.
System: Two Fluid Spray
<Etching in First Step>
Flow rate: 30 mL/min
Pressure: 200 kPa
Time: 30 sec
<Etching in Second Step>
Flow rate: 20 mL/min
Pressure: 200 kPa
Time: 10 sec
The resist pattern was peeled using the obtained substrate under
the following conditions, the pattern formed of the water-soluble
resin film was removed by being washed with water and heated at
100.degree. C. for 10 minutes, moisture remaining on the organic
semiconductor film was removed, and the film was dried so that the
damage during the process was repaired, thereby obtaining a
substrate on which the organic semiconductor film was
patterned.
System: paddle
Peeling solution: propylene glycol monomethyl ether
Time: 60 sec
Synthesis Example 17
Synthesis of Specific Resin C9
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (8.10 g), t-BuMA (11.00 g), MA (2.60 g), and V-601
(0.840 g, 2.37% by mole with respect to monomers) were dissolved in
PGMEA (18.12 g) and the mixture was added dropwise to the solution
for 2 hours. After dropwise addition, the solution was stirred for
4 hours and the reaction was finished. In this manner, a specific
resin C9 represented by the following Structural Formula was
obtained. The weight average molecular weight was 20000.
##STR00093##
Synthesis Example 18
Synthesis of Specific Resin C10
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. PMA (7.50 g), t-BuMA (11.00 g), MA (2.60 g), and V-601
(0.840 g, 2.37% by mole with respect to monomers) were dissolved in
PGMEA (18.12 g) and the mixture was added dropwise to the solution
for 2 hours. After dropwise addition, the solution was stirred for
4 hours and the reaction was finished. In this manner, a specific
resin C10 represented by the following Structural Formula was
obtained. The weight average molecular weight was 21000.
##STR00094##
Synthesis Example 19
Synthesis of tBocMMA
tBocMMA can be synthesized by reacting an alcohol with a carboxylic
halide compound under basic conditions and reacting the resultant
with a carboxylic acid compound under basic conditions using the
same method as described in JP2005-331918A.
Synthesis Example 20
Synthesis of Specific Resin C11
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (8.10 g), the above-described tBocMMA (11.70 g),
MA (4.20 g), and V-601 (0.840 g, 2.42% by mole with respect to
monomers) were dissolved in PGMEA (18.12 g) and the mixture was
added dropwise to the solution for 2 hours. After dropwise
addition, the solution was stirred for 4 hours and the reaction was
finished. In this manner, a specific resin C11 represented by the
following structural formula was obtained. The weight average
molecular weight was 19500.
##STR00095##
Synthesis Example 20
Synthesis of Specific Resin C12
PGMEA (18.12 g) was added to a three-necked flask and the
temperature was increased to 86.degree. C. under a nitrogen
atmosphere. BzMA (9.25 g), THFMA (12.30 g), and V-601 (0.730 g,
2.41% by mole with respect to monomers) were dissolved in PGMEA
(18.12 g) and the mixture was added dropwise to the solution for 2
hours. After dropwise addition, the solution was stirred for 4
hours and the reaction was finished. In this manner, a specific
resin C12 was obtained. The weight average molecular weight was
15000.
##STR00096##
<Preparation of Water-Soluble Resin Composition and Chemically
Amplified Photosensitive Resin Composition>
The following water-soluble resin composition and photosensitive
resin composition were mixed with each other to obtain a uniform
solution, the water-soluble resin composition was filtered using a
nylon filter having a pore size of 0.8 .mu.m, the chemically
amplified photosensitive resin composition was filtered using a
polytetrafluoroethylene filter having a pore size of 0.03 .mu.m,
and thus water-soluble resin compositions and chemically amplified
photosensitive resin compositions of Examples 22 to 45 and
Comparative Examples 13 to 20 were respectively prepared.
[Water-Soluble Resin Compositions]
Water-soluble resin listed in Table 3: parts by mass listed in
Table 3 Acetylenol E00 (manufactured by Kawaken Fine Chemical Co.,
Ltd.): 0.1 parts by mass
Solvent listed in Table 3: parts by mass listed in Table 3
Glycerin (only Example 25, manufactured by Tokyo Chemical Industry
Co., Ltd.): 0.45 parts by mass
[Chemically Amplified Photosensitive Resin Compositions]
Resin listed in Table 3: parts by mass listed in Table 3
Photoacid generator listed in Table 3: parts by mass listed in
Table 3
Basic compound listed in Table 3: parts by mass listed in Table
3
PF-6320 (manufactured by OMNOVA Solutions Inc.): 0.05 parts by
mass
Propylene glycol monomethyl ether acetate (manufactured by Wako
Pure Chemical Industries, Ltd.): 85 parts by mass
TABLE-US-00009 TABLE 3 Water-soluble resin composition Chemically
amplified photosensitive resin composition Water- Photoacid Decom-
Basic soluble resin Solvent Resin generator position compound Parts
Parts Parts Parts Parts Molar Parts rate of Parts by by by by by
absorption by photoacid by Type mass Type mass Type mass Type mass
Type mass Type pKa coefficient ma- ss generator Type mass Example
22 A5 13 Water 86.9 C9 14.3 D7 -14 5300 0.5 A E2 0.15 Example 23 A6
15 Water 84.9 C9 14.3 D7 -14 5300 0.5 A E2 0.15 Example 24 A7 13
Water 86.9 C9 14.3 D7 -14 5300 0.5 A E2 0.15 Example 25 A5 7 A6 7
Water 85.9 C9 14.3 D7 -14 5300 0.5 A E2 0.15 Example 26 A5 14.55
Water 84.9 C9 14.3 D7 -14 5300 0.5 A E2 0.15 Example 27 A5 13 Water
82.4 IPA 4.5 C9 14.3 D7 -14 5300 0.5 A E2 0.15 Example 28 A5 13
Water 86.9 C9 14.3 D7 -14 5300 0.5 A E2 0.15 Example 29 A5 13 Water
86.9 C9 14.3 D7 -14 5300 0.5 A E3 0.15 Example 30 A5 13 Water 86.9
C9 14.3 D7 -14 5300 0.5 A E4 0.15 Example 31 A5 13 Water 86.9 C10
14.3 D7 -14 5300 0.5 A E2 0.15 Example 32 A5 13 Water 86.9 C10 14.3
D7 -14 5300 0.5 A E3 0.15 Example 33 A5 13 Water 86.9 C10 14.3 D7
-14 5300 0.5 A E4 0.15 Example 34 A5 13 Water 86.9 C11 14.3 D7 -14
5300 0.5 A E2 0.15 Example 35 A5 13 Water 86.9 C11 14.3 D7 -14 5300
0.5 A E3 0.15 Example 36 A5 13 Water 86.9 C11 14.3 D7 -14 5300 0.5
A E4 0.15 Example 37 A5 13 Water 86.9 C9 14.3 D8 -14 6600 0.5 A E2
0.15 Example 38 A5 13 Water 86.9 C9 14.3 D9 -8 7000 0.5 A E2 0.15
Example 39 A5 13 Water 86.9 C9 14.3 D10 -8 5500 0.5 A E2 0.15
Example 40 A5 13 Water 86.9 C9 14.3 D7 -14 5300 0.5 A E5 0.15
Example 41 A5 13 Water 86.9 C9 14.3 D8 -14 6600 0.5 A E5 0.15
Example 42 A5 13 Water 86.9 C9 14.3 D7 -14 5300 0.5 A E6 0.15
Example 43 A5 13 Water 86.9 C9 14.3 D8 -14 6600 0.5 A E6 0.15
Example 44 A5 13 Water 86.9 C12 14.3 D7 -14 5300 0.5 A E2 0.15
Example 45 A5 13 Water 86.9 C12 14.3 D8 -14 6600 0.5 A E2 0.15
Comparative A5 13 Water 86.9 C12 14.3 D11 -14 450 0.5 B E2 0.15
Example 13 Comparative A5 13 Water 86.9 C9 14.3 D11 -14 450 0.5 B
E2 0.15 Example 14 Comparative A5 13 Water 86.9 C9 14.3 D12 -5.8
200 0.5 C E2 0.15 Example 15 Comparative A5 13 Water 86.9 C9 14.3
D13 -5.8 360 0.5 B E2 0.15 Example 16 Comparative A5 13 Water 86.9
C9 14.3 D14 -5.8 190 0.5 C E2 0.15 Example 17 Comparative A5 13
Water 86.9 C9 14.3 D15 -2.8 3400 0.5 B E2 0.15 Example 18
Comparative A5 13 Water 86.9 C9 14.3 D16 -5.8 1 0.5 C E2 0.15
Example 19 Comparative A5 13 Water 86.9 C9 14.3 D17 -5.8 600 0.5 B
E2 0.15 Example 20
In addition, abbreviations in Table 3 are as follows.
<Water-Soluble Resin>
IPA: isopropyl alcohol (manufactured by Wako Pure Chemical
Industries, Ltd.)
A5: polyvinyl alcohol (PVA203, manufactured by KURARAY CO., LTD.,
sp value=25.8 MPa).sup.1/2)
A6: polyvinyl pyrrolidone (polyvinyl pyrrolidone K-30, manufactured
by Nippon Shokubai Co., Ltd., sp value=22.5 MPa).sup.1/2)
A7: pullulan (manufactured by Hayashibara Co., Ltd., sp value: 27.8
MPa).sup.1/2)
<Photoacid Generator>
D7: NT-1TF (trifluoromethane sulfonic acid (pKa=-14)-generated
5-membered ring imide sulfonate type, molar absorption
coefficient=5300 L/(molcm), manufactured by San-Apro Ltd.)
D8: NT-3TF (trifluoromethane sulfonic acid (pKa=-14)-generated
5-membered ring imide sulfonate type, molar absorption
coefficient=6600 L/(molcm), manufactured by San-Apro Ltd.)
D9: the following structure (heptafluoropropane sulfonic acid
(pKa=-8)-generated oxime sulfonate type, molar absorption
coefficient=7000 L/(molcm))
D10: the following structure (heptafluoropropane sulfonic acid
(pKa=-8)-generated 5-membered ring imide sulfonate type, molar
absorption coefficient=5500 L/(molcm))
D11: NT-2TF (trifluoromethane sulfonic acid (pKa=-14)-generated
6-membered ring imide sulfonate type, molar absorption
coefficient=450 L/(molcm), manufactured by San-Apro Ltd.)
D12: CGI-1905 (the following structure, nonafluorobutane sulfonic
acid (pKa=-5.8)-generated oxime sulfonate type, molar absorption
coefficient=200 L/(molcm), manufactured by BASF Japan Ltd.)
D13: CGI-1906 (the following structure, nonafluorobutane sulfonic
acid (pKa=-5.8)-generated oxime sulfonate type, molar absorption
coefficient=360 L/(molcm), manufactured by BASF Japan Ltd.)
D14: CGI-1907 (the following structure, nonafluorobutane sulfonic
acid (pKa=-5.8)-generated oxime sulfonate type, molar absorption
coefficient=190 L/(molcm), manufactured by BASF Japan Ltd.)
D15: Irgacure PAG-121 (the following structure, paratoluene
sulfonic acid (pKa=-2.8)-generated oxime sulfonate type, molar
absorption coefficient=3400 L/(molcm), manufactured by BASF Japan
Ltd.)
D16: NDI-109 (the following structure, nonafluorobutane sulfonic
acid (pKa=-5.8)-generated 5-membered ring imide sulfonate type,
molar absorption coefficient=1 L/(molcm), manufactured by Midori
Kagaku Co., Ltd.)
D17: CPI-310NF (nonafluorobutane sulfonic acid (pKa=-5.8)-generated
type, ionic, molar absorption coefficient=600 L/(molcm),
manufactured by San-Apro Ltd.)
<Resin>
E2: 2,6-diisopropylaniline (primary amine, manufactured by Tokyo
Chemical Industry Co., Ltd.)
E3: 2,4,6-tri-tert-butylaniline (primary amine, manufactured by
Tokyo Chemical Industry Co., Ltd.)
E4: hexylamine (primary amine, manufactured by Tokyo Chemical
Industry Co., Ltd.)
E5: N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea (secondary
amine, manufactured by Inabata & Co., Ltd.)
E6: N,N-dimethyl-4-aminopyridine (tertiary amine, manufactured by
Tokyo Chemical Industry Co., Ltd.)
##STR00097##
<Organic Semiconductor Film Formation>
An organic semiconductor film was formed by spin-coating a glass
substrate having dimensions of 5 cm.sup.2 with an organic
semiconductor coating solution formed of a composition described
below and drying the glass substrate at 130.degree. C. for 10
minutes. The film thickness was 150 nm.
P3HT (manufactured by Sigma-Aldrich Co., LLC.): 10% by mass
PCBM (manufactured by Sigma-Aldrich Co., LLC.): 10% by mass
Chloroform (manufactured by Wako Pure Chemical Industries, Ltd.):
80% by mass
<Process of Coating Substrate with Water-Soluble Resin
Composition>
A water-soluble resin film was formed by spin-coating the substrate
on which the organic semiconductor film was formed with the
water-soluble resin composition and drying the substrate at
100.degree. C. for 1 minute. The film thickness was 1 .mu.m.
<Process of Preparing Mask Pattern of Resin on Water-Soluble
Resin Film>
The substrate on which the water-soluble resin film was formed was
spin-coated with a chemically amplified photosensitive resin
composition formed of a composition listed in the table above and
dried at 100.degree. C. for 1 minute. The film thickness was 1
.mu.m. Next, the film was exposed to light under the condition of
200 mJ/cm.sup.2 using a parallel light exposure device of the
i-line. Subsequently, the film was heated at 120.degree. C. for 1
minute and developed using butyl acetate, thereby obtaining a mask
pattern.
<Process of Patterning Organic Semiconductor by Performing Dry
Etching>
The obtained substrate was dry-etched, and the mask pattern, the
water-soluble resin film of a non-mask pattern portion, and the
organic semiconductor film of the non-mask pattern portion were
removed. The dry etching was performed under the same conditions as
those described above.
<Process of Dissolving Remaining Water-Soluble Resin in Water
and Removing the Same>
The obtained substrate was washed with water, a pattern formed of
the water-soluble resin film was removed, the substrate was heated
at 100.degree. C. for 10 minutes, moisture remaining on the organic
semiconductor film was removed, and the damage during the process
was repaired, thereby obtaining a substrate on which the organic
semiconductor film was patterned.
<Evaluation>
<<In-Plane Uniformity of Water-Soluble Resin Film>>
Evaluation was performed under the same conditions as those of the
evaluation of the in-plane uniformity of the above-described
water-soluble resin film.
<<Pattern Shape of Resist Film>>
Evaluation was performed under the same conditions as those of the
evaluation of the pattern shape of the above-described resist
film.
<<Pattern Shape of Organic Semiconductor Film>>
Evaluation was performed under the same conditions as those of the
evaluation of the pattern shape of the above-described organic
semiconductor film.
<<Surface Form of Water-Soluble Resin Film>>
The coating surface form of the water-soluble resin film was
observed using an optical microscope. Evaluation was performed
based on the following criteria.
A: No cracks were not observed over the entire surface.
B: Cracks were partially generated at the time of film formation of
the chemically amplified photosensitive resin composition.
C: No cracks were observed over the entire surface immediately
after coating.
<<Storage Stability of Chemically Amplified Photosensitive
Resin Composition>>
The prepared chemically amplified photosensitive resin composition
was left in a thermostatic tank at 50.degree. C. for one week, and
the optimum exposure value (exposure value in which a difference
from a design pattern line width became the smallest), before and
after the composition was left, was calculated by observing a
pattern formed using a contact aligner with a scanning electron
microscope. Evaluation was performed based on the following
criteria.
A: Variation in the optimum exposure value was less than
.+-.3%.
B: Variation in the optimum exposure value was .+-.3% to less than
10%.
C: Variation in the optimum exposure value was .+-.10% or
greater.
TABLE-US-00010 TABLE 4 In-plane Pattern shape uniformity of Pattern
of organic water-soluble shape of semiconductor resin film resist
film film Example 22 A A A Example 23 B A A Example 24 B A A
Example 25 A A A Example 26 A A A Example 27 A A A Example 28 A A A
Example 29 A A A Example 30 A A A Example 31 A A A Example 32 A A A
Example 33 A A A Example 34 A A A Example 35 A A A Example 36 A A A
Example 37 A A A Example 38 A B B Example 39 A B B Example 40 A A A
Example 41 A A A Example 42 A A A Example 43 A A A Example 44 A A B
Example 45 A A B Comparative Example 13 A C B Comparative Example
14 A C B Comparative Example 15 A C C Comparative Example 16 A C B
Comparative Example 17 A C C Comparative Example 18 A C B
Comparative Example 19 A C C Comparative Example 20 A C B
TABLE-US-00011 TABLE 5 Storage stability of Surface form of
chemically amplified water-soluble photosensitive resin film resin
composition Example 22 A A Example 23 B A Example 24 B A Example 25
A A Example 26 A A Example 27 A A Example 28 A A Example 29 A A
Example 30 A A Example 31 A A Example 32 A A Example 33 A A Example
34 A A Example 35 A A Example 36 A A Example 37 A A Example 38 A A
Example 39 A A Example 40 A B Example 41 A B Example 42 A B Example
43 A B Example 44 A B Example 45 A B Comparative Example 13 A B
Comparative Example 14 A C Comparative Example 15 A C Comparative
Example 16 A A Comparative Example 17 A C Comparative Example 18 A
A Comparative Example 19 A C Comparative Example 20 A C
As listed in the table above, in Examples, the water-soluble resin
film was formed to have an excellent surface form, patterning
properties of the resist film were excellent, and storage stability
was excellent. Accordingly, it could be understood that a fine
pattern of the organic semiconductor was able to be formed.
Meanwhile, in Comparative Examples, the in-plane uniformity, the
patterning properties, or storage stability was degraded. For this
reason, it could be understood that a fine pattern of the organic
semiconductor was unlikely to be able to be formed.
The same as in Examples and Comparative Examples above was
performed except that organic semiconductor coating solutions were
changed to the following. As a result, it was recognized that the
same tendencies as those in Examples and Comparative Examples were
shown.
<Composition A of Organic Semiconductor Coating Solution>
TABLE-US-00012 TIPS pentacene (manufactured by Sigma-Aldrich 5
parts by mass Co., LLC.) Toluene (manufactured by Sigma-Aldrich
Co., LLC.) 95 parts by mass
<Composition B of Organic Semiconductor Film>
TABLE-US-00013 MEH-PPV (manufactured by Sigma-Aldrich Co., 10 parts
by mass LLC.) Toluene (manufactured by Sigma-Aldrich Co., LLC.) 90
parts by mass
<Composition C of Organic Semiconductor Coating Solution>
TABLE-US-00014 PEDOT/PSS (manufactured by Sigma-Aldrich Co., 100
parts by mass LLC., 1.3 mass % aqueous dispersion liquid)
The same as in Examples and Comparative Examples above was
performed except that wet etching was performed using the following
etching solutions in place of dry etching. As a result, it was
recognized that the same tendencies as those in Examples and
Comparative Examples were shown.
<Etching Solution 1 in First Step>
Water 100% by mass
<Etching Solution 1 in Second Step>
Propylene glycol monomethyl ether 100% by mass
<Etching Solution 2 in First Step>
2-propanol 100% by mass
<Etching Solution 2 in Second Step>
Propylene glycol monomethyl ether 100% by mass
<Etching Solution 3 in First Step>
Water 100% by mass
<Etching Solution 3 in Second Step>
3-methyl-1-butanol 100% by mass
The water-soluble resin film of a non-mask pattern portion and the
organic semiconductor film of the non-mask pattern portion were
removed by performing wet etching on the substrate under the
following conditions.
System: Two Fluid Spray
<Etching in First Step>
Flow rate: 30 mL/min
Pressure: 200 kPa
Time: 30 sec
<Etching in Second Step>
Flow rate: 20 mL/min
Pressure: 200 kPa
Time: 10 sec
The resist pattern was peeled using the obtained substrate under
the following conditions, the pattern formed of the water-soluble
resin film was removed by being washed with water and heated at
100.degree. C. for 10 minutes, moisture remaining on the organic
semiconductor film was removed, and the film was dried so that the
damage during the process was repaired, thereby obtaining a
substrate on which the organic semiconductor film was
patterned.
System: paddle
Peeling solution: propylene glycol monomethyl ether
Time: 60 sec
EXPLANATION OF REFERENCES
1: substrate
2: organic semiconductor film
3: water-soluble resin film
4: mask pattern
* * * * *